CN108473869B - CaCO3 treatment for O2 removal - Google Patents

CaCO3 treatment for O2 removal Download PDF

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Publication number
CN108473869B
CN108473869B CN201780005276.0A CN201780005276A CN108473869B CN 108473869 B CN108473869 B CN 108473869B CN 201780005276 A CN201780005276 A CN 201780005276A CN 108473869 B CN108473869 B CN 108473869B
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containing material
calcium carbonate
acid
magnesium carbonate
carbonate
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CN108473869A (en
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S·瑞恩特什
M·韦尔克
P·A·C·加纳
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Omya International AG
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Omya International AG
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    • B01J20/043—Carbonates or bicarbonates, e.g. limestone, dolomite, aragonite
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    • A23B—PRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
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Abstract

The invention relates to the use of a surface-treated calcium carbonate-containing material and/or a magnesium carbonate-containing material as an oxygen scavenger; wherein the surface treatment agent is selected from the group consisting of: ascorbic acid and/or salts thereof, gallic acid and/or salts thereof, unsaturated fatty acids and/or salts thereof, elemental iron, iron (II) salts and iron (II) oxides, iron (II, III) oxides and mixtures thereof; and wherein the total weight of the surface treatment agent on the total surface area of the at least one calcium carbonate-comprising material and/or magnesium carbonate-comprising material is from 0.01 to 40mg/m2, based on the at least one calcium carbonate-comprising material and/or magnesium carbonate-comprising material.

Description

Removing O2CaCO of3Treatment of
The present application relates to the use of a surface-treated calcium carbonate-containing material and/or a magnesium carbonate-containing material as oxygen scavenger.
Various methods are known, such as frozen storage, refrigeration, vacuum packaging and packaging under an inert atmosphere, to reduce or prevent the formation and/or growth of oomycetes, bacteria and higher organisms such as insects which tend to disturb the preservation of food products. However, most oomycetes, bacteria and higher organisms require oxygen to develop and grow. Thus, one very suitable method of preventing mold and rot in food applications is to use oxygen scavengers or oxygen absorbers to absorb or "trap" oxygen in the environment (e.g., gaseous environment). For example, such oxygen scavengers are used in food applications, especially food packaging applications, to prevent mildew and rot of food products such as vegetables, fruits, meat and fish, cheese or processed foods such as bread and pastry, potato chips, peanuts or prepared meals.
Another application is in the cosmetic field. Cream, gel or essence, and cosmetic, powder, etc., and can be used for human body or skin. Many active substances incorporated therein can be destroyed by oxidation, and therefore, it is desirable to package and market these cosmetics so that relatively small amounts of oxygen come into contact with the active substances. This is possible if oxygen scavengers or oxygen absorbers are used in the cosmetic or cosmetic package to absorb or "trap" oxygen in the environment (e.g., gaseous environment).
Another application is the protection of packaged metal articles. One problem with metal articles is corrosion, which is the reaction of the metal with an oxidant, such as oxygen, resulting in electrochemical oxidation of the metal, also known as rusting in the case of iron. Therefore, it is desirable to package the metal articles with an oxygen scavenger or oxygen getter that absorbs or "traps" oxygen in the environment in order to prevent oxidation of the metal articles.
Various materials comprising oxygen scavenging or absorbing properties are known to the skilled person. For example, US 4,524,015 relates to a composition comprising at least one ascorbic acid compound selected from ascorbic acid, ascorbate salts and mixtures thereof, an alkali metal carbonate, an iron compound, carbon black and water. The particulate oxygen absorber is produced by mixing the compounds, for example in a granulator, and blending them.
EP 1916276 relates to a packaging material comprising a metal protection component comprising a volatile corrosion inhibitor, a desiccant and an oxygen scavenger. The oxygen scavenger may comprise a triazole, such as benzotriazole.
US2014/0288224 relates to non-fiber reinforced thermoplastic molding compositions. The composition comprises an elemental metal, such as iron, as an oxygen scavenger.
EP 0320085 relates to a boiling water oxygen scavenger and method of use. The oxygen scavenger comprises ascorbic acid neutralized with diethylaminoethanol.
However, not only is it important that the materials used as oxygen scavengers are inexpensive, non-toxic and readily available materials, they must also provide efficient oxygen (O) removal2)。
In view of the foregoing, there is a continuing need for materials with improved properties that can be used as oxygen scavengers as compared to prior art materials that have been used as oxygen scavengers.
Accordingly, it is an object of the present invention to provide a catalyst which can be used as an oxygen scavenger and which provides high efficiency in oxygen removal (O)2) The material of (1). In particular, it is an object of the present invention to provide oxygen scavengers which can be used as oxygen scavengers providing improved oxygen scavenging (O) compared to known oxygen scavenger materials2) The material of (1).
It is another object of the present invention to provide a material that can be used as an oxygen scavenger, is non-toxic and is easy to handle.
It is another object of the present invention to provide oxygen scavengers which are useful as oxygen scavengers and provide long lasting oxygen (O) removal2) Materials capable of removing large amounts of oxygen from the environment per unit of scavenger are acted upon and/or added. It is another object of the present invention to provide materials having high oxygen scavenging efficiency. It is another object of the present invention to reduce the amount of active material required to obtain good oxygen scavenging activity.
The foregoing and other objects are solved by the subject-matter as defined herein in the independent claims.
According to one aspect of the present invention, there is provided the use of a surface-treated calcium carbonate-containing material and/or a magnesium carbonate-containing material as an oxygen scavenger; wherein the surface treatment agent is selected from the group consisting of: ascorbic acid and/or its salt, gallic acid and/or its salt, unsaturated fatty acid and/or its salt, elemental iron, iron (II) salt and pharmaceutical composition containing the sameIron (II) oxide, iron (II, III) oxide and mixtures thereof; and wherein the total weight of the surface treatment agent on the total surface area of the at least one calcium carbonate-comprising material and/or magnesium carbonate-comprising material is from 0.01 to 40mg/m, based on the total surface area of the at least one calcium carbonate-comprising material and/or magnesium carbonate-comprising material2。
Advantageous embodiments of the invention are defined in the respective dependent claims.
According to one embodiment, the calcium carbonate-comprising material and/or the magnesium carbonate-comprising material is selected from the group consisting of: ground calcium carbonate, preferably marble, limestone and/or chalk, precipitated calcium carbonate, preferably aragonite, calcite and/or aragonite, dolomite and mixtures thereof, more preferably the at least one calcium carbonate-containing material and/or magnesium carbonate-containing material is selected from the group consisting of: dolomitic marble, magnesite marble, limestone, chalk and mixtures thereof, and most preferably the at least one calcium carbonate containing material and/or magnesium carbonate containing material is ground calcium carbonate.
According to one embodiment, the at least one calcium carbonate-comprising material and/or magnesium carbonate-comprising material has a specific surface area (BET) of 0.5 to 150m, as measured according to ISO 9277:2010 using the nitrogen and BET method2A/g, preferably from 1 to 60m2G, and more preferably 1.5 to 15m2/g。
According to one embodiment, the total weight of the surface treatment agent on the total surface area of the at least one surface-treated calcium carbonate-comprising material and/or magnesium carbonate-comprising material is from 0.1 to 40mg/m, based on the total surface area of the at least one calcium carbonate-comprising material and/or magnesium carbonate-comprising material2Preferably 0.5 to 20mg/m2And more preferably 0.7 to 15mg/m2。
According to one embodiment, the surface treated calcium carbonate-comprising material and/or the magnesium carbonate-comprising material has a moisture absorption susceptibility in the range of 0.05 to 20mg/g, preferably 0.1 to 15mg/g and more preferably 0.2 to 10 mg/g.
According to one embodiment, the unsaturated fatty acid is selected from the group consisting of: oleic acid, linoleic acid, linolenic acid, crotonic acid, myristoleic acid, palmitoleic acid, hexadecenoic acid, elaidic acid, octadecenoic acid, gadoleic acid, erucic acid, nervonic acid, eicosadienoic acid, docosadienoic acid, pinolenic acid (pinoleic acid), eleostearic acid, melissic acid, dihomo-y-linolenic acid, eicosatrienoic acid, stearidonic acid, arachidonic acid, adrenic acid, octadecanoic acid, eicosapentaenoic acid, oxazoic acid (ozobondo acid), sardinic acid (sardine acid), tetracosapentaenoic acid, docosahexaenoic acid, herring acid, salts of these acids, and mixtures thereof, preferably the unsaturated fatty acid is oleic acid or linoleic acid.
According to one embodiment, the iron is the volume median particle size d50Particulate powdered iron in the range of 5nm to 10 μm, preferably 10nm to 2 μm, and more preferably 30nm to 500 nm.
According to one embodiment, the calcium carbonate-comprising material and/or the magnesium carbonate-comprising material is additionally treated with another additive, preferably with a dispersant, such as a polyacrylate dispersant, a binder and/or an activator, more preferably with a binder and/or an activator.
According to one embodiment, the total volume of oxygen reacted per gram of surface treatment agent is in the range of 0.01 to 10mL per day per gram of surface treatment agent and preferably in the range of 0.1 to 8mL per day per gram of surface treatment agent and more preferably in the range of 0.4 to 6mL per day per gram of surface treatment agent, wherein the reaction with oxygen is carried out with 500g of dry surface treated calcium carbonate containing material and/or magnesium carbonate containing material in a volume of 7L, in an enclosed air filled dryer at normal pressure.
According to one embodiment, the surface-treated calcium carbonate-comprising material and/or the magnesium carbonate-comprising material further comprises at least one extender being a hydrophobizing agent at least partially covering the surface-treated calcium carbonate-comprising material and/or the magnesium carbonate-comprising material, wherein the total weight of the at least one hydrophobizing agent over the total surface area of the surface-treated material is from 0.001 to 10mg/m based on the at least one calcium carbonate-comprising material and/or the magnesium carbonate-comprising material2Preferably 0.001 to 9mg/m2More preferably 0.01 to 8mg/m2And most preferably 0.1 to 4mg/m2。
According to one embodiment, the surface-treated calcium carbonate-comprising material and/or magnesium carbonate-comprising material comprises at least one extender being a hydrophobic agent selected from the group consisting of: total amount of carbon atoms being C4To C24By a total amount of carbon atoms in the substituents selected to be at least C2To C30Mono-substituted succinic anhydrides consisting of mono-substituted succinic anhydrides of linear, branched, aliphatic and cyclic groups and/or reaction products thereof, phosphate blends of one or more phosphoric monoesters and/or reaction products thereof with one or more phosphoric diesters and/or reaction products thereof, polyhydrosiloxanes and reaction products thereof, inert silicone oils, preferably polydimethylsiloxanes and mixtures thereof.
According to one embodiment, the surface-treated calcium carbonate-comprising material and/or the magnesium carbonate-comprising material is used as oxygen scavenger in a polymer composition, a coating, preferably in a polymer or a paper coating, more preferably in a paper coating, a food application, a filter and/or a cosmetic application, preferably in a food application and more preferably in a food packaging application.
It is to be understood that for purposes of the present invention, the following terms have the following meanings.
By "calcium carbonate-containing material" is meant in the meaning of the present invention a material which is a source of calcium carbonate and is preferably selected from ground calcium carbonate, precipitated calcium carbonate, dolomite and mixtures thereof. The "calcium carbonate-containing material" of the present invention is not defined as natural ground or precipitated calcium carbonate with carbon dioxide and one or more H3O+"surface-treated calcium carbonate" of the reaction product of an ion donor, in which carbon dioxide is passed through H3O+The ion donor treatment is formed in situ and/or supplied from an external source. H3O+The ion donor is Brookfield acid (B)
Figure BDA0001711391020000051
acid) And/or an acid salt.
By "magnesium carbonate-containing material" is meant in the meaning of the present invention a material that is the source of magnesium carbonate.
"ground calcium carbonate" (GCC) in the meaning of the present invention is calcium carbonate obtained from natural sources, such as limestone, marble or chalk, and which is processed by wet and/or dry processes, such as grinding, sieving and/or fractionation, for example by cyclones or classifiers.
"precipitated calcium carbonate" (PCC) in the meaning of the present invention is a synthetic material, usually obtained by precipitation after reaction of carbon dioxide and calcium hydroxide (slaked lime) in an aqueous environment or by precipitation from calcium and carbonate sources in water. Alternatively, precipitated calcium carbonate may be a product of, for example, the introduction of calcium and carbonate, calcium chloride and sodium carbonate in an aqueous environment. PCC may have a crystalline form of vaterite, calcite, or aragonite. PCC is described, for example, in EP 2447213 a1, EP 2524898 a1, EP 2371766 a1, EP 2840065 a1 or WO 2013/142473 a 1.
The term "dry" or "dried" material is understood to mean a material having 0.001 to 20 weight-% water, based on the total weight of the surface-treated calcium carbonate-comprising material and/or the magnesium carbonate-comprising material. The% water (equal to "water content") was determined gravimetrically. By "drying" in the sense of the present invention is meant that the heating is carried out until the water content of the surface-treated calcium carbonate-comprising material and/or the magnesium carbonate-comprising material is in the range of from 0.001 to 20 wt. -%, based on the total weight of the surface-treated calcium carbonate-comprising material and/or the magnesium carbonate-comprising material.
The "particle size" of particulate material, e.g., calcium carbonate-containing material and/or magnesium carbonate-containing material herein, is used in terms of its particle size dxThe distribution of (c). Wherein the value dxDenotes the diameter, with respect to which x% by weight of the particles have a diameter smaller than dx. This means, for example, d20The value is the particle size below which 20 weight-% of all particles are smaller. Thus d50The value is the weight median particle size, i.e. 50 weight-% of all particles is larger, while the remaining 50 weight-% is smaller than the particlesSub-size. For the purposes of the present invention, unless otherwise specified, the particle size diameter is designated as weight median particle size d50。d98The value is the particle size below which 98 weight-% of all particles are smaller. By using a Sedigraph from Micromeritics Instrument CorporationTMThe 5100 or 5120 apparatus determines particle size. The methods and apparatus are known to the skilled person and are generally used for determining the particle size of fillers and pigments. Measured at 0.1 weight-% Na4P2O7In an aqueous solution of (a). The samples were dispersed and sonicated using a high speed stirrer.
Evaluation of volume median particle diameter d Using a Malvern Mastersizer 2000laser diffraction System50. D measured using a Malvern Mastersizer 2000laser diffraction System50Or d98The values represent diameter values such that 50% or 98% of the particles have a diameter smaller than this value, respectively. The raw data obtained by the measurement were analyzed using Mie theory, and the particle refractive index was 1.57 and the absorption index was 0.005.
The "Specific Surface Area (SSA)" of a calcium carbonate-comprising material and/or a magnesium carbonate-comprising material in the meaning of the present invention is defined as the surface area of the calcium carbonate-comprising material and/or the magnesium carbonate-comprising material divided by its mass. As used herein, specific surface area is measured by nitrogen adsorption using BET isotherm (ISO 9277:2010) and is expressed in m2The/g is specified.
The term "surface area" or "outer surface" in the meaning of the present invention refers to the surface of the nitrogen accessible calcium carbonate-containing material and/or magnesium carbonate-containing material particles used for measuring BET according to ISO 9277: 2010. In this connection, it should be noted that the amount of the surface treatment agent according to claim 1 required for complete saturation of the surface area is defined as a monolayer concentration. Higher concentrations can thus be selected by forming a bilayer or multilayer structure on the surface of the calcium carbonate-comprising material particles.
For the purposes of the present invention, the term "viscosity" or "Brookfield viscocity" refers to Brookfield viscosity. For this purpose, the Brookfield viscosity is measured with a Brookfield DV-III Ultra viscometer at 24 ℃. + -. 3 ℃ and 100rpm using the appropriate spindle of a Brookfield RV spindle device and is specified in mPas. Once the spindle is inserted into the sample, the measurement is started at a constant rotation speed of 100 rpm. The reported brookfield viscosity values are the values shown 60 seconds after the start of the measurement. From his technical knowledge, the skilled person will select a spindle from the Brookfield RV-spindle device that is suitable for the viscosity range to be measured. For example, for a viscosity range of 200 to 800mPa · s, a spindle No. 3 may be used, for a viscosity range of 400 to 1600mPa · s, a spindle No. 4 may be used, for a viscosity range of 800 to 3200mPa · s, a spindle No. 5 may be used, for a viscosity range of 1000 to 2000000mPa · s, a spindle No. 6 may be used, and for a viscosity range of 4000 to 8000000mPa · s, a spindle No. 7 may be used.
For the purposes of this application, a "water insoluble" material is defined as a material that, when 100g of the material is mixed with 100g of deionized water and filtered at 20 ℃ on a filter having a pore size of 0.2 μm to remove liquid filtrate, provides less than or equal to 0.1g of recovered solid material after evaporation of 100g of the liquid filtrate at 95 to 100 ℃ at ambient pressure. A "water soluble" material is defined as a material that, when 100g of the material is mixed with 100g of deionized water and filtered at 20 ℃ on a filter having a pore size of 0.2 μm to remove liquid filtrate, provides more than 0.1g of recovered solid material after evaporation of 100g of the liquid filtrate at 95 to 100 ℃ at ambient pressure.
A "suspension" or "slurry" in the meaning of the present invention comprises insoluble solids and a solvent or liquid, preferably water, and optionally also additives, and generally contains a large amount of solids, and thus is more viscous and can have a higher density than the liquid formed therefrom.
The term "surface treatment agent" according to the present invention is an agent for treating the surface of the at least one calcium carbonate-comprising material and/or magnesium carbonate-comprising material. The surface treatment agent of the present invention is selected from the group consisting of: ascorbic acid and/or salts thereof, gallic acid and/or salts thereof, unsaturated fatty acids and/or salts thereof, elemental iron, iron (II) salts and iron (II) oxides, iron (II, III) oxides and mixtures thereof.
In the context of the present invention a "surface-treated calcium carbonate-comprising material and/or magnesium carbonate-comprising material" comprises at least a calcium carbonate-comprising material and/or a magnesium carbonate-comprising material, which has been brought into contact with at least one surface treatment agent according to the present invention in order to obtain a treatment layer on at least a part of the surface of the calcium carbonate-comprising material and/or the magnesium carbonate-comprising material. Thus, the term "treatment layer" refers to a layer comprising a surface treatment agent and reaction products thereof on at least a portion of the surface of the calcium carbonate-containing material and/or the magnesium carbonate-containing material. The term "reaction product" in the meaning of the present invention refers to a product obtained by contacting the at least one calcium carbonate-comprising material and/or magnesium carbonate-comprising material with at least one surface treatment agent according to the present invention.
The "oxygen scavenger" or "oxygen getter" according to the present invention is capable of absorbing or "capturing" oxygen in the ambient atmosphere.
The term "absorbent" according to the present invention refers to the ability to "scavenge" and maintain the retention of scavenging species over time in separation independent of any material concentration gradient mechanism, but only dependent on absorption saturation. The term "absorption" in the context of the present invention includes the physicochemical mechanisms of absorption and adsorption.
The term "solid" according to the present invention refers to a material that is solid at Standard Ambient Temperature and Pressure (SATP), which refers to a temperature of 298.15K (25 ℃) and an absolute pressure of exactly 100000 Pa (1 bar, 14.5psi, 0.98692 atm). The solids may be in the form of powders, tablets, granules, flakes, and the like.
The term "ambient pressure" according to the present invention refers to the Standard Ambient Temperature Pressure (SATP), which refers to an absolute pressure of exactly 100000 Pa (1 bar, 14.5psi, 0.98692 atm). The term "reduced pressure" refers to a pressure that is less than "ambient pressure".
When the term "comprising" is used in the present description and claims, it does not exclude other non-specified elements of primary or secondary functional importance. For the purposes of the present invention, the term "consisting of … …" is considered to be a preferred embodiment of the term "comprising". If a group is defined below as comprising at least a certain number of embodiments, this should also be understood as disclosing a group preferably consisting of only these embodiments.
Whenever the terms "including" or "having" are used, these terms are intended to be equivalent to the "comprising" defined above.
When referring to a singular noun, the indefinite or definite article, e.g. "a", "an" or "the", is used, unless specifically stated otherwise, to include a plural of that noun.
Terms such as "available" or "definable" and "obtained" or "defined" may be used interchangeably. For example, it is meant that the term "obtaining" is not intended to imply that, for example, an embodiment must be obtained in the order of, for example, the steps following the term "obtaining," unless the context clearly dictates otherwise, although the term "obtaining" or "defining" as a preferred embodiment always includes such limited understanding.
It has been found according to the invention that a calcium carbonate-containing material and/or a magnesium carbonate-containing material that has been surface-treated in some way can be used as an oxygen scavenger. Thus, according to the present invention, there is provided the use of a surface treated calcium carbonate-comprising material and/or a magnesium carbonate-comprising material as an oxygen scavenger, wherein the surface treatment agent is selected from the group consisting of: ascorbic acid and/or salts thereof, gallic acid and/or salts thereof, unsaturated fatty acids and/or salts thereof, elemental iron, iron (II) salts and iron (II) oxides, iron (II, III) oxides and mixtures thereof; and wherein the total weight of the surface treatment agent on the total surface area of the at least one calcium carbonate-comprising material and/or magnesium carbonate-comprising material is from 0.01 to 40mg/m, based on the total surface area of the at least one calcium carbonate-comprising material and/or magnesium carbonate-comprising material2。
In the following, details and preferred embodiments of the inventive use of the surface-treated calcium carbonate-comprising material and/or the magnesium carbonate-comprising material as oxygen scavenger will be explained in more detail.
The surface-treated calcium carbonate-containing material and/or magnesium carbonate-containing material used according to the invention is a calcium carbonate-containing material and/or magnesium carbonate-containing material that has been surface-treated with a surface-treating agent. In the following, the calcium carbonate-containing material and/or the magnesium carbonate-containing material and the surface treatment agent will be defined in more detail.
Calcium carbonate-containing material and/or magnesium carbonate-containing material
According to one embodiment of the invention, the surface-treated calcium carbonate-comprising material and/or the magnesium carbonate-comprising material comprises at least one calcium carbonate-comprising material and/or a magnesium carbonate-comprising material.
The expression "at least one" calcium carbonate-comprising material and/or magnesium carbonate-comprising material means that one or more, for example two or three, calcium carbonate-comprising materials and/or magnesium carbonate-comprising materials may be present in the surface-treated calcium carbonate-comprising material and/or magnesium carbonate-comprising material. According to a preferred embodiment, only one calcium carbonate-containing material and/or magnesium carbonate-containing material is present among the surface-treated calcium carbonate-containing material and/or magnesium carbonate-containing material.
According to one embodiment of the invention, the "calcium carbonate-comprising material and/or magnesium carbonate-comprising material" may be a mineral material or a synthetic material, the content of calcium carbonate and/or magnesium carbonate of which is at least 30 weight-%, preferably 40 weight-%, more preferably 50 weight-%, even more preferably 75 weight-%, even more preferably 90 weight-%, and most preferably 95 weight-%, based on the dry weight of the calcium carbonate-comprising material and/or the magnesium carbonate-comprising material.
According to one embodiment of the invention, the surface-treated calcium carbonate-comprising material and/or magnesium carbonate-comprising material comprises a calcium carbonate-and magnesium carbonate-comprising material. According to another embodiment of the invention, the surface-treated calcium carbonate-comprising material and/or the magnesium carbonate-comprising material comprises a calcium carbonate-comprising material. According to another embodiment of the invention, the surface-treated calcium carbonate-comprising material and/or the magnesium carbonate-comprising material comprises a magnesium carbonate-comprising material.
According to one embodiment, the at least one calcium carbonate-comprising material consists of calcium carbonate. According to a preferred embodiment, the at least one calcium carbonate-comprising material consists of calcium carbonate.
The at least one calcium carbonate-comprising material and/or magnesium carbonate-comprising material is preferably in the form of a particulate material. According to one embodiment of the present invention, the weight median particle size d of the at least one calcium carbonate-comprising material and/or magnesium carbonate-comprising material50The value is in the range of 0.1 to 7 μm. For example, the weight median particle size d of the at least one calcium carbonate-comprising material50Is 0.25 μm to 5 μm and preferably 0.7 μm to 4 μm.
According to one embodiment of the present invention, the at least one calcium carbonate-comprising material and/or magnesium carbonate-comprising material may have a top cut value (d) of ≦ 15 μm98). For example, the at least one calcium carbonate-comprising material and/or magnesium carbonate-comprising material may have a top cut value (d) of 12.5 μm or less, preferably 10 μm or less and most preferably 7.5 μm or less98)。
According to another embodiment of the invention, the specific surface area of the calcium carbonate-comprising material and/or the magnesium carbonate-comprising material is from 0.5 to 150m, as measured according to ISO 9277:2010 using the nitrogen and BET method2A/g, preferably from 1 to 60m2G, and more preferably 1.5 to 15m2/g。
According to a preferred embodiment of the invention, the calcium carbonate-comprising material and/or the magnesium carbonate-comprising material is selected from the group consisting of: ground calcium carbonate, preferably marble, limestone and/or chalk, precipitated calcium carbonate, preferably aragonite, calcite and/or aragonite, dolomite and mixtures thereof, more preferably the at least one calcium carbonate-containing material and/or magnesium carbonate-containing material is selected from the group consisting of: dolomitic marble, magnesite marble, limestone, chalk and mixtures thereof, and most preferably the at least one calcium carbonate containing material and/or magnesium carbonate containing material is ground calcium carbonate.
Natural or Ground Calcium Carbonate (GCC) is understood to be made in the form of naturally occurring calcium carbonate, taken from sedimentary rocks such as limestone or chalk, or from metamorphic marbles, eggshells or shells. Calcium carbonate is known to exist as three types of crystalline polymorphs: calcite, aragonite and vaterite. Calcite is the most common crystal polymorph and is considered to be the most stable crystalline form of calcium carbonate. Less common is aragonite, which has a discrete or clustered acicular orthorhombic crystal structure. Spherulite is the rarest polymorphic form of calcium carbonate and is generally unstable. Ground calcium carbonate is almost exclusively a calcite polymorph, which is said to be triangular-rhombohedral and represents the most stable form of calcium carbonate polymorph. The term "source" of calcium carbonate in the meaning of the present application refers to the naturally occurring mineral material from which the calcium carbonate is obtained. The source of calcium carbonate may comprise other naturally occurring components such as magnesium carbonate, aluminosilicates and the like.
In general, the grinding of the natural ground calcium carbonate may be a dry or wet grinding step and may be carried out with any conventional grinding apparatus, for example under conditions such that comminution is mainly caused by impact with secondary bodies, i.e. in one or more of the following apparatuses: ball mills, rod mills, vibratory mills, roll mills, centrifugal impact mills, vertical bead mills, attritors, pin mills, hammer mills, pulverizers, choppers, deblockers, cutters, or other such equipment known to the skilled person. In case the calcium carbonate-comprising mineral material comprises a wet heavy calcium carbonate-comprising mineral material, the grinding step may be performed under conditions such that autogenous grinding is performed and/or by horizontal ball milling and/or other methods known to the skilled person. The wet processed ground calcium carbonate-containing mineral material thus obtained can be washed and dewatered by known methods, for example by flocculation, filtration or forced evaporation before drying. The subsequent drying step (if necessary) may be carried out in a single step, e.g. spray drying, or in at least two steps. It is also common for such mineral materials to undergo a beneficiation step (e.g. flotation, bleaching or magnetic separation step) to remove impurities.
According to one embodiment of the invention, the source of natural or Ground Calcium Carbonate (GCC) is selected from marble, chalk, limestone or mixtures thereof. Preferably, the source of ground calcium carbonate is marble, and more preferably dolomitic marble and/or magnesite marble. According to one embodiment of the invention, the GCC is obtained by dry milling. According to another embodiment of the invention, the GCC is obtained by wet grinding and subsequent drying.
In the meaning of the present invention "dolomite" is of chemical composition CaMg (CO)3)2 (“CaCO3·MgCO3") a calcium carbonate-containing mineral, i.e., a calcium carbonate-magnesium mineral. The dolomite mineral may contain at least 30.0 weight-% MgCO, based on the total weight of the dolomite3Preferably above 35.0 weight-%, and more preferably above 40.0 weight-% of MgCO3。
According to one embodiment of the invention, the calcium carbonate comprises one type of ground calcium carbonate. According to another embodiment of the invention, the calcium carbonate comprises a mixture of two or more types of ground calcium carbonate selected from different sources.
"precipitated calcium carbonate" (PCC) in the meaning of the present invention is a synthetic material, usually obtained by precipitation after reaction of carbon dioxide with lime in an aqueous environment or by precipitation from sources of calcium and carbonate ions in water or by combining calcium and carbonate ions, such as CaCl2And Na2CO3Obtained by precipitation from solution. Other possible processes for producing PCC are lime soda, or Solvay process, wherein PCC is a by-product of ammonia production. Precipitated calcium carbonate exists in three main crystalline forms: calcite, aragonite and vaterite, and many different polymorphs (crystal habit) exist for each of these crystalline forms. Calcite has a triangular structure with typical crystallographic habit, such as scalenohedral (S-PCC), rhombohedral (R-PCC), hexagonal prism, axial plane, colloidal (C-PCC), cubic and prismatic (P-PCC). Aragonite is a orthorhombic structure with a typical crystal habit of twinned hexagonal prisms, as well as various elongated prisms, curved leaves, steep pyramids, chisel crystals, branching trees, and coral or worm-like forms. The spherulites belong to the hexagonal system. The PCC slurry obtained may be mechanically dewatered and dried.
According to one embodiment of the invention, the precipitated calcium carbonate is a precipitated calcium carbonate preferably comprising an aragonite, vaterite or calcite mineralogical form or a mixture thereof.
According to one embodiment of the invention, the calcium carbonate comprises one type of precipitated calcium carbonate. According to another embodiment of the present invention, the calcium carbonate comprises a mixture of two or more precipitated calcium carbonates selected from different crystal forms and different polymorphs of precipitated calcium carbonate. For example, the at least one precipitated calcium carbonate may comprise one PCC selected from S-PCC and one PCC selected from R-PCC.
According to a preferred embodiment of the present invention, the at least one calcium carbonate-containing material and/or magnesium carbonate-containing material is ground calcium carbonate.
The at least one calcium carbonate-containing material, preferably ground calcium carbonate and/or precipitated calcium carbonate, is preferably in the form of a particulate material. According to one embodiment of the present invention, the weight median particle size d of the at least one calcium carbonate-containing material, preferably ground calcium carbonate and/or precipitated calcium carbonate50The value is in the range of 0.1 to 7 μm. For example, the weight median particle size d of the at least one calcium carbonate-comprising material50Is 0.25 μm to 5 μm and preferably 0.7 μm to 4 μm.
According to one embodiment of the present invention, the at least one calcium carbonate-containing material, preferably ground calcium carbonate and/or precipitated calcium carbonate, may have a top cut value (d) of ≦ 15 μm98). For example, the at least one calcium carbonate-comprising material may have a top cut value (d) of 12.5 μm or less, preferably 10 μm or less and most preferably 7.5 μm or less98)。
According to another embodiment of the present invention, the specific surface area of the ground calcium carbonate and/or precipitated calcium carbonate is from 0.5 to 150m, as measured according to ISO 9277:2010 using the nitrogen and BET method2A/g, preferably from 1 to 60m2G, and most preferably 1.5 to 15m2/g。
According to one embodiment of the invention, the calcium carbonate-comprising material and/or the magnesium carbonate-comprising material is additionally treated with another additive. In a preferred embodiment of the invention, the calcium carbonate-comprising material and/or the magnesium carbonate-comprising material is additionally treated with a dispersant, a binder and/or an activator and most preferably with a binder and/or an activator. Conventional dispersants, binders and activators known to the skilled worker can be used. Preferred dispersants are, for example, polyacrylate dispersants.
Surface treating agent
According to the invention, the surface treatment agent is selected from the group consisting of: ascorbic acid and/or salts thereof, gallic acid and/or salts thereof, unsaturated fatty acids and/or salts thereof, elemental iron, iron (II) salts and iron (II) oxides, iron (II, III) oxides and mixtures thereof.
According to one embodiment of the invention, the surface-treated calcium carbonate-comprising material and/or the magnesium carbonate-comprising material comprises at least one surface treatment agent. The expression "at least one" surface treatment agent means that one or more, for example two or three, surface treatment agents may be present at the surface of the calcium carbonate-comprising material and/or the magnesium carbonate-comprising material. According to a preferred embodiment, only one surface treatment agent is present at the surface of the calcium carbonate-comprising material and/or the magnesium carbonate-comprising material.
According to one embodiment of the invention, the surface treatment agent is ascorbic acid. Ascorbic acid is also known as vitamin C and has the formula C6H8O6. For example, the ascorbic acid can be L-ascorbic acid, also known as (5R) -5- [ (1S) -1, 2-dihydroxyethyl]-3, 4-dihydroxy-2 (5H) -furanone, and/or D-erythorbic acid, also known as (5R) -5- [ (1R) -1, 2-dihydroxyethyl]-3, 4-dihydroxyfuran-2 (5H) -one. According to a preferred embodiment, the ascorbic acid is L-ascorbic acid. In one embodiment, the treating agent is L-ascorbic acid or D-erythorbic acid, preferably L-ascorbic acid. In an alternative embodiment, the treating agents are L-ascorbic acid and D-erythorbic acid.
Additionally or alternatively, the treatment agent is an ascorbate salt.
The ascorbate salt is preferably a compound selected from the group consisting of: sodium, potassium, calcium, palmitate and stearate salts thereof. For example, the treating agent is a sodium, potassium and/or calcium salt of ascorbic acid.
According to one embodiment of the invention, the surface treatment agent is gallic acid. Gallic acid is also known as 3,4, 5-trihydroxybenzoate and has the formula C7H6O5。
Additionally or alternatively, the treatment agent is a gallic acid salt.
The gallic acid salt is preferably a compound selected from the group consisting of: sodium, potassium, calcium, magnesium and lithium salts thereof.
Additionally or alternatively, the at least one surface treatment agent is selected from unsaturated fatty acids.
The term "unsaturated fatty acid" in the meaning of the present invention refers to a straight-chain or branched, unsaturated organic compound consisting of carbon and hydrogen. The organic compound also contains a carboxyl group disposed at a terminal end of the carbon skeleton.
The unsaturated fatty acid is preferably selected from the group consisting of: oleic acid, linoleic acid, linolenic acid, crotonic acid, myristoleic acid, palmitoleic acid, hexadecenoic acid, elaidic acid, octadecenoic acid, gadoleic acid, erucic acid, nervonic acid, eicosadienoic acid, docosadienoic acid, pinolenic acid, eleostearic acid, melissic acid, dihomo-y-linolenic acid, eicosatrienoic acid, stearidonic acid, arachidonic acid, adrenic acid, octadecapentaenoic acid, eicosapentaenoic acid, oxazoic acid, sabobutyric acid, tetracosapentaenoic acid, docosahexaenoic acid, herring acid, salts of these acids, and mixtures thereof, preferably the unsaturated fatty acid is oleic acid or linoleic acid. Most preferably, the surface treatment agent which is an unsaturated fatty acid is oleic acid and/or linoleic acid, preferably oleic acid or linoleic acid, most preferably linoleic acid.
Additionally or alternatively, the surface treatment agent is an unsaturated fatty acid salt.
The term "unsaturated fatty acid salt" refers to an unsaturated fatty acid in which the active acid group is partially or fully neutralized. The term "partially neutralized" unsaturated fatty acid means that the degree of neutralization of the active acid groups is in the range of 40 to 95 mole-%, preferably 50 to 95 mole-%, more preferably 60 to 95 mole-% and most preferably 70 to 95 mole-%. The term "fully neutralized" unsaturated fatty acid means that the degree of neutralization of the active acid groups is > 95 mole-%, preferably > 99 mole-%, more preferably > 99.8 mole-% and most preferably 100 mole-%. Preferably, the active acid radical is partially or fully neutralized.
The unsaturated fatty acid salt is preferably a compound selected from the group consisting of: sodium, potassium, calcium, magnesium, lithium, strontium, primary, secondary, tertiary and/or ammonium salts thereof, whereby the amine salts are linear or cyclic. For example, the surface treatment agent is a salt of oleic acid and/or linoleic acid, preferably a salt of oleic acid or linoleic acid, most preferably a salt of linoleic acid.
The unsaturated fatty acid salt is preferably obtained by treating the unsaturated fatty acid with a base before the surface treatment so as to obtain its corresponding salt.
The base may be selected from potassium hydroxide, lithium hydroxide, ammonium hydroxide and/or sodium hydroxide, and is preferably sodium hydroxide.
The addition of the at least one base to the unsaturated fatty acid may be achieved by any conventional means known to the skilled person. Preferably, the addition may be carried out under mixing conditions. The skilled person will vary these mixture conditions such as mixing speed and temperature depending on his process equipment.
The base may be added to the unsaturated fatty acid in an amount in the range of from 0.1 to 100 mol-%, preferably in the range of from 1 to 98 mol-%, more preferably in the range of from 10 to 95 mol-%, and most preferably in the range of from 40 to 95 mol-%, based on the unsaturated fatty acid.
According to one embodiment of the invention, the surface treatment agent is elemental iron, an iron (II) salt and an iron (II) containing oxide and/or an iron (II, III) containing oxide.
The term "elemental iron" according to the invention refers to the chemical element designated as Fe. Elemental iron is a solid at Standard Ambient Temperature and Pressure (SATP), which refers to a temperature of 298.15K (25 ℃) and an absolute pressure of exactly 100000 Pa (1 bar, 14.5psi, 0.98692 atm). The elemental iron may be in the form of powder, tablets, granules, flakes, and the like.
For example, the element iron is the volume median particle size d50Powdered iron in the form of particles in the range of 5 to 10 μm. Preferably, the element iron is the volume median particle size d50Powdered iron in the form of particles in the range of 10nm to 2 μm, and more preferably 30nm to 500 nm.
In one embodiment, the elemental iron is powdered iron in the form of particles in the nm size range. For example, the element iron is the volume median particle size d50Particulate powdered iron in the range of 10nm to 300nm, preferably 20 to 200nm, and more preferably 30nm to 100 nm.
The term "iron (II) salt" according to the present invention refers to a ferrous salt in which the iron has the oxidation number II. The oxidation number or oxidation state according to the present invention is an indication of the degree of oxidation (electron loss) of iron in iron salts. A possible iron (II) salt is iron bromide (FeBr)2) Iron chloride (FeCl)2) Iron fluoride (FeCl)2) Iron iodide (FeI)2) Iron molybdate (FeMoO)4) Iron oxalate (FeC)2O4) Ferrous sulfate (FeSO)4) (anhydrous), iron (II) sulfate monohydrate, iron (II) sulfate heptahydrate, ammonium iron (II) sulfate hexahydrate, and iron (Fe (BF) tetrafluoroborate4)2) And potassium hexacyanoferrate (K)4Fe(CN)6). Preferably, the treatment agent being an iron (II) salt is selected from the group consisting of: iron (II) sulfate monohydrate, iron (II) sulfate heptahydrate, ammonium iron (II) sulfate hexahydrate, ferric chloride (II), and mixtures thereof. Most preferably, the treating agent which is an iron (II) salt Is Iron (II) sulfate heptahydrate and/or iron (II) chloride, preferably iron (II) sulfate heptahydrate or iron (II) chloride, most preferably iron (II) sulfate heptahydrate.
The term "iron (II) -containing oxide" according to the present invention refers to ferrous oxide wherein the iron has the oxidation number II. The oxidation number or oxidation state according to the present invention is an indicator of the degree of oxidation (electron loss) of iron in iron oxide. One possible iron (II) oxide is FeO.
The term "iron (II, III) -containing oxide" according to the present invention refers to ferrous oxide wherein the iron has oxidation numbers II and III. The oxidation number or oxidation state according to the present invention is an indicator of the degree of oxidation (electron loss) of iron in iron oxide. One possible iron (II, III) oxide is Fe3O4。
According to the invention, the total weight of the surface treatment agent on the total surface area of the at least one calcium carbonate-comprising material and/or magnesium carbonate-comprising material is from 0.01 to 40mg/m, based on the at least one calcium carbonate-comprising material and/or magnesium carbonate-comprising material2。
According to one embodiment of the present invention, the total weight of surface treatment agent on the total surface area of the at least one surface-treated calcium carbonate-comprising material and/or magnesium carbonate-comprising material is from 0.1 to 40mg/m, based on the at least one calcium carbonate-comprising material and/or magnesium carbonate-comprising material2Preferably 0.5 to 20mg/m2And more preferably 0.7 to 15mg/m2。
By "total weight" according to the invention is meant the weight of surface treatment agent located on the total surface area of the calcium carbonate-comprising material and/or the magnesium carbonate-comprising material.
Surface-treated calcium carbonate-containing material and/or magnesium carbonate-containing material
The surface-treated calcium carbonate-containing material and/or magnesium carbonate-containing material according to the present invention is a calcium carbonate-containing material and/or magnesium carbonate-containing material that has been treated with a surface treatment agent selected from the group consisting of: ascorbic acid and/or salts thereof, gallic acid and/or salts thereof, unsaturated fatty acids and/or salts thereof, elemental iron, iron (II) salts and iron (II) oxides, iron (II, III) oxides and mixtures thereof. The total weight of the surface treatment agent on the total surface area of the at least one calcium carbonate-and/or magnesium carbonate-containing material is from 0.01 to 40mg/m, based on the at least one calcium carbonate-and/or magnesium carbonate-containing material2。
According to one embodiment, the surface-treated calcium carbonate-comprising material and/or the magnesium carbonate-comprising material according to the invention is in the form of a suspension.
According to a preferred embodiment, the surface-treated calcium carbonate-comprising material and/or the magnesium carbonate-comprising material according to the invention is in solid form, e.g. in the form of a powder, a tablet, a granule, a flake, etc. Preferably, the surface-treated calcium carbonate-comprising material and/or the magnesium carbonate-comprising material according to the invention is in the form of a powder.
The surface-treated calcium carbonate-comprising material and/or the magnesium carbonate-comprising material according to the invention is preferably in the form of a particulate material. According to one embodiment of the present invention, the weight median particle size d of the surface-treated calcium carbonate-comprising material and/or the magnesium carbonate-comprising material according to the invention50The value is in the range of 0.1 to 7 μm. For example, the weight median particle size d of the surface-treated calcium carbonate-comprising material50Is 0.25 μm to 5 μm and preferably 0.7 μm to 4 μm.
According to one embodiment of the invention, the surface-treated calcium carbonate-comprising material and/or the magnesium carbonate-comprising material according to the invention may have a top cut value (d) of ≦ 15 μm98). For example, the surface-treated calcium carbonate-comprising material and/or magnesium carbonate-comprising material according to the invention may have a top cut value (d) of 12.5 μm or less, preferably 10 μm or less and most preferably 7.5 μm or less98)。
According to another embodiment of the invention, the surface-treated calcium carbonate-comprising material and/or magnesium carbonate-comprising material according to the invention has a specific surface area of 0.5 to 150m, as measured according to ISO 9277:2010 using the nitrogen and BET method2A/g, preferably from 1 to 60m2G, and more preferably 1.5 to 15m2/g。
According to another embodiment of the present invention, the total weight of surface treatment agent on the total surface area of the at least one surface-treated calcium carbonate-comprising material and/or magnesium carbonate-comprising material is from 0.1 to 40mg/m, based on the at least one calcium carbonate-comprising material and/or magnesium carbonate-comprising material2Preferably 0.5 to 20mg/m2And more preferably 0.7 to 15mg/m2。
Furthermore, the treated calcium carbonate-comprising material of the invention has a specific susceptibility to moisture absorption. Preferably, the moisture absorption susceptibility of the treated calcium carbonate is such that its total surface moisture content is 100mg/g or less, more preferably 60mg/g or less and most preferably less than 40mg/g of the treated dried calcium carbonate. For example, the moisture absorption susceptibility of the treated calcium carbonate is in the range of 0.05 to 20mg/g, preferably 0.1 to 15mg/g and more preferably 0.2 to 10 mg/g.
According to one embodiment of the invention, the surface-treated calcium carbonate-comprising material and/or the magnesium carbonate-comprising material further comprises at least one extender which is a hydrophobic agent.
The at least one hydrophobizing agent may be any agent known to the skilled person that is capable of forming a hydrophobically treated layer on at least a portion of the accessible surface area of the surface-treated calcium carbonate-containing material and/or magnesium carbonate-containing material.
The term "at least one" hydrophobizing agent in the meaning of the present invention means that the hydrophobizing agent comprises, preferably consists of, one or more hydrophobizing agents.
In one embodiment of the invention, the at least one supplement being a hydrophobic agent comprises, preferably consists of, one hydrophobic agent. Optionally, the at least one hydrophobic agent comprises, preferably consists of, two or more hydrophobic agents. For example, the at least one hydrophobic agent comprises, preferably consists of, two or three hydrophobic agents.
Preferably, the at least one hydrophobizing agent comprises, more preferably consists of, one hydrophobizing agent.
According to one embodiment of the invention, the surface-treated calcium carbonate-comprising material and/or the magnesium carbonate-comprising material comprises at least one extender which is a hydrophobic agent selected from the group consisting of: total amount of carbon atoms being C4To C24By a total amount of carbon atoms in the substituents selected to be at least C2To C30Mono-substituted succinic anhydrides consisting of mono-substituted succinic anhydrides of linear, branched, aliphatic and cyclic groups and/or reaction products thereof, phosphate blends of one or more phosphoric monoesters and/or reaction products thereof with one or more phosphoric diesters and/or reaction products thereof, polyhydrosiloxanes and reaction products thereof, inert silicone oils, preferably polydimethylsiloxanes and mixtures thereof.
Aliphatic carboxylic acids suitable for treating the surface-treated calcium carbonate obtained in step c) are, for example, aliphatic linear or branched carboxylic acids having from 4 to 24 carbon atoms.
Aliphatic linear or branched carboxylic acids in the meaning of the present invention may be selected from one or more linear, branched, saturated, unsaturated and/or alicyclic carboxylic acids. Preferably, the aliphatic linear or branched carboxylic acid is a monocarboxylic acid, i.e. the aliphatic linear or branched carboxylic acid is characterized by the presence of a single carboxyl group. The carboxyl group is placed at the end of the carbon skeleton.
In one embodiment of the present invention, the aliphatic linear or branched carboxylic acid is selected from saturated unbranched carboxylic acids, i.e. the aliphatic linear or branched carboxylic acid is preferably selected from the group consisting of: carboxylic acids consisting of butyric, valeric, caproic, enanthic, caprylic, pelargonic, capric, undecanoic, lauric, tridecanoic, myristic, pentadecanoic, palmitic, margaric, stearic, nonadecanoic, arachidic, heneicosanoic, behenic, tricosanoic, lignoceric acids and mixtures thereof.
In another embodiment of the present invention, the aliphatic linear or branched carboxylic acid is selected from the group consisting of: caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and mixtures thereof. Preferably, the aliphatic linear or branched carboxylic acid is selected from the group consisting of: myristic acid, palmitic acid, stearic acid and mixtures thereof.
For example, the aliphatic linear or branched carboxylic acid is stearic acid.
Additionally or alternatively, the at least one extender which is a hydrophobic agent is prepared by adding at least C to the total amount of carbon atoms in the substituent2To C30And/or phosphate blends of one or more phosphoric monoesters and one or more phosphoric diesters.
Monosubstituted succinic anhydride and/or phosphate blends and suitable compounds for coatings are described in EP 2722368 a1 and EP 2770017 a1, which are hereby incorporated by reference.
Alternatively or additionally, the at least one hydrophobic agent is an inert silicone oil such as a polydialkylsiloxane, for example as described in US 2004/0097616 a 1.
The most preferred inert silicone oils are selected from the group consisting of: polydimethylsiloxanes, preferably dimethylpolysiloxanes, polydiethylsiloxanes and polymethylphenylsiloxanes and/or mixtures thereof.
The inert silicone oil is preferably present in an amount such that the total amount of said inert silicone oil on at least a part of the surface treated calcium carbonate-comprising material and/or magnesium carbonate-comprising material is less than 1000 ppm, preferably less than 800ppm and most preferably less than 600 ppm. For example, the total amount of inert silicone oil on at least a part of the surface-treated calcium carbonate-comprising material and/or magnesium carbonate-comprising material is from 100 to 1000 ppm, more preferably from 200 to 800ppm and most preferably from 300 to 600ppm, for example from 400 to 600 ppm.
Additionally or alternatively, the at least one hydrophobic agent is a polyhydrosiloxane, preferably poly (methylhydrosiloxane).
Additionally or alternatively, the at least one hydrophobic agent is a fatty aldehyde. Fatty aldehydes for use in coatings are described in EP 2390285 a 1.
Preferably, the total weight of the at least one hydrophobizing agent over the total surface area of the surface-treated calcium carbonate-comprising material and/or the magnesium carbonate-comprising material is lower than the total weight of the treating agent as a treatment layer on at least a part of the surface of the calcium carbonate-comprising material and/or the magnesium carbonate-comprising material.
According to one embodiment of the invention, the surface-treated calcium carbonate-comprising material and/or the magnesium carbonate-comprising material further comprises at least one hydrophobizing agent at least partially covering the surface-treated calcium carbonate-comprising material and/or the magnesium carbonate-comprising material, wherein the total weight of the at least one hydrophobizing agent over the total surface area of the surface-treated calcium carbonate-comprising material and/or the magnesium carbonate-comprising material is from 0.001 to 10mg/m, based on the total surface area of the at least one calcium carbonate-comprising material and/or the magnesium carbonate-comprising material2Preferably 0.001 to 9mg/m2More preferably 0.01 to 8mg/m2And most preferably 0.1 to 4mg/m2。
Method for producing surface-treated calcium-and/or magnesium-carbonate-containing materials
The surface-treated calcium carbonate-containing material and/or magnesium carbonate-containing material according to the present invention is a calcium carbonate-containing material and/or magnesium carbonate-containing material that has been treated with a surface treatment agent selected from the group consisting of: ascorbic acid and/or salts thereof, gallic acid and/or salts thereof, unsaturated fatty acids and/or salts thereof, elemental iron, iron (II) salts and iron (II) oxides, iron (II, III) oxides and mixtures thereof. The total weight of the surface treatment agent on the total surface area of the at least one calcium carbonate-comprising material and/or magnesium carbonate-comprising material is from 0.01 to 40mg/m, based on the at least one calcium carbonate-comprising material and/or magnesium carbonate-comprising material2。
Methods for preparing the surface-treated calcium carbonate-comprising material and/or the magnesium carbonate-comprising material according to the invention are known to the skilled person. For example, one method of treating a calcium carbonate-containing material and/or a magnesium carbonate-containing material comprises the steps of:
a) providing a calcium carbonate-comprising material and/or a magnesium carbonate-comprising material,
b) providing a composition selected from the group consisting of: ascorbic acid and/or a salt thereof, gallic acid and/or a salt thereof, unsaturated fatty acids and/or a salt thereof, elemental iron, iron (II) salts and treatment agents comprising iron (II) oxide, iron (II, III) oxide and mixtures thereof, and
c) combining the calcium carbonate-containing material and/or the magnesium carbonate-containing material of step a) with the treating agent of step b) in one or more steps under mixing at a temperature of 20 to 120 ℃ such that the total weight of the treating agent added is 0.01 to 40mg/m based on the at least one calcium carbonate-containing material and/or magnesium carbonate-containing material2。
Characterization of step a): provision of calcium carbonate-containing material and/or magnesium carbonate-containing material
According to step a), a calcium carbonate-comprising material and/or a magnesium carbonate-comprising material is provided, as defined above.
It will be appreciated that the calcium carbonate-comprising material and/or the magnesium carbonate-comprising material may be provided in the form of an aqueous suspension or in a dry form.
If the calcium carbonate-comprising material and/or the magnesium carbonate-comprising material is provided in the form of an aqueous suspension, the aqueous suspension preferably has a solids content in the range of from 5 to 80 weight-%, based on the total weight of the aqueous suspension. According to a preferred embodiment, the solids content of the aqueous suspension is in the range of from 10 to 78 weight-%, more preferably in the range of from 15 to 75 weight-% and most preferably in the range of from 15 to 75 weight-%, based on the total weight of the aqueous suspension.
The term "aqueous" suspension refers to a system wherein the liquid phase comprises, preferably consists of, water. However, the term does not exclude that the liquid phase of the aqueous suspension comprises a minor amount of at least one water-soluble organic solvent selected from the group comprising methanol, ethanol, acetone, acetonitrile, tetrahydrofuran and mixtures thereof. If the aqueous suspension comprises at least one water-soluble organic solvent, the liquid phase of the aqueous suspension comprises the at least one water-soluble organic solvent in an amount of 0.1 to 40.0 wt-%, preferably 0.1 to 30.0 wt-%, more preferably 0.1 to 20.0 wt-% and most preferably 0.1 to 10.0 wt-%, based on the total weight of the liquid phase of the aqueous suspension. For example, the liquid phase of the aqueous suspension consists of water.
According to a preferred embodiment, the aqueous suspension consists of water and a calcium carbonate-containing material and/or a magnesium carbonate-containing material.
Optionally, the surface-treated aqueous suspension of calcium carbonate comprises further additives.
Additionally or alternatively, the aqueous suspension of calcium carbonate-containing material and/or magnesium carbonate-containing material comprises a dispersing agent, such as a polyacrylate.
Preferably, the calcium carbonate-comprising material and/or the magnesium carbonate-comprising material provided in step a) is a dried calcium carbonate-comprising material and/or a magnesium carbonate-comprising material.
For example, the water content of the calcium carbonate-comprising material and/or the magnesium carbonate-comprising material provided in step a) is below 10.0 weight-%, based on the dry weight of the calcium carbonate-comprising material and/or the magnesium carbonate-comprising material provided in step a).
In one embodiment, the water content of the calcium carbonate-comprising material and/or the magnesium carbonate-comprising material provided in step a) is between 0.01 and 10.0 weight-%, preferably between 0.01 and 8.0 weight-%, and more preferably between 0.01 and 6.0 weight-%, based on the dry weight of the calcium carbonate-comprising material and/or the magnesium carbonate-comprising material provided in step a).
Characterization of step b): provision of a treating agent
According to step b), as defined above, a treatment agent is provided.
The treating agent is preferably in "liquid" or "molten" form. For example, the treatment agent is a (pure) liquid at 25 ℃ and ambient pressure. Optionally, the treating agent is in molten form.
If the treating agent is in solid form, it may also be dissolved/dispersed/suspended in a solvent and added as a solution or suspension or dispersion to the calcium carbonate-comprising material and/or the magnesium carbonate-comprising material in step c), i.e. as a liquid.
The solvent which can be used for diluting/dissolving/dispersing/suspending the treating agent may be water and/or a water-miscible organic solvent, for example, an organic solvent such as methanol, ethanol, n-butanol, isopropanol, n-propanol, and a mixture thereof. According to a preferred embodiment, the solvent consists of water. According to another preferred embodiment, the solvent is a mixture of water and at least one water-miscible organic solvent. Preferably, the solvent is a mixture of water and ethanol and more preferably the ratio of the water to ethanol mixture is from 2:1 to 1:2 based on the weight of the solvent, and most preferably the ratio of the water to ethanol mixture is 1:1 based on the weight of the solvent.
According to one embodiment, the solids content of the diluted/dispersed suspension/dispersion comprising solvent and treatment agent is in the range of from 0.1 to 60 weight-%, preferably in the range of from 1 to 40 weight-%, more preferably in the range of from 1.5 to 30 weight-%, and most preferably in the range of from 2 to 25 weight-%, based on the total weight of the suspension/dispersion.
According to another embodiment, the amount of the treatment agent in the diluted/dissolved/dispersed/suspended solution suspension/dispersion comprising solvent and treatment agent is in the range of from 0.1 to 60 weight-%, preferably in the range of from 1 to 40 weight-%, more preferably in the range of from 1.5 to 30 weight-%, and most preferably in the range of from 2 to 25 weight-%, based on the total weight of the solution/suspension/dispersion.
According to another embodiment, the treatment agent or the diluted/dissolved/dispersed solution/suspension/dispersion comprising the solvent and the at least one treatment agent is preheated before carrying out the combining step c). That is, the treating agent or the diluted/dissolved/dispersed solution/suspension/dispersion comprising the solvent and the treating agent is treated at a temperature of from 30 to 120 ℃, preferably from 45 to 115 ℃, more preferably from 50 to 105 ℃ and most preferably from 80 to 100 ℃ before the combining step c) is carried out.
The treatment time for carrying out the preheating of the treating agent or the diluting/dissolving/dispersing solution/suspension/dispersion containing the solvent and the treating agent is 30 minutes or less, preferably 20 minutes or less and more preferably 15 minutes or less.
According to another embodiment, the treatment agent or the diluted/dissolved/dispersed solution/suspension/dispersion comprising the solvent and the treatment agent is preheated at a temperature of 30 to 120 ℃, preferably 45 to 115 ℃, more preferably 50 to 105 ℃ and most preferably 80 to 100 ℃ for 30 minutes or less, preferably 20 minutes or less and more preferably 15 minutes or less before the addition step c) is carried out.
In one embodiment, the preheating of the treating agent or the diluted/dissolved/dispersed solution/suspension/dispersion comprising the solvent and the treating agent is carried out at a temperature approximately equal to the temperature achieved during the combining step c).
The term "equal" temperature in the meaning of the present invention refers to a preheating temperature which is at most 20 ℃, preferably at most 15 ℃, more preferably 10 ℃ and most preferably at most 5 ℃ lower or higher than the temperature achieved during the combining step c).
The preheating of the treating agent or the diluted/dissolved/dispersed solution/suspension/dispersion comprising the solvent and the treating agent is preferably carried out under mixing conditions. The skilled person will vary these mixture conditions (e.g. configuration of the mixing pallets and mixing speed) depending on his process equipment.
Optionally, the surface treatment agent may be added as a solid. For example, if the surface treatment agent is elemental iron, it may be added as a solid, for example as a powder.
Characterization of step c): combining a calcium carbonate-containing material and/or a magnesium carbonate-containing material with a treating agent
Combining the calcium carbonate-containing material and/or the magnesium carbonate-containing material of step a) with the treating agent of step b) according to step c) in one or more steps under mixing at a temperature of 1 to 200 ℃ such that the total weight of the added surface treating agent is 0.01 to 40mg/m, based on the calcium carbonate-containing material and/or the magnesium carbonate-containing material of step a)2。
It is necessary to add a treating agent to the calcium carbonate-comprising material and/or the magnesium carbonate-comprising material of step a) such that the total weight of the added treating agent is from 0.01 to 40mg/m, based on the calcium carbonate-comprising material and/or the magnesium carbonate-comprising material of step a)2。
For example, a treatment agent is added to the calcium carbonate containing material and/or the magnesium carbonate containing material of step a) such that the total weight of the treatment agent added in step c) is from 0.1 to 40mg/m, based on the calcium carbonate containing material and/or the magnesium carbonate containing material of step a)2And preferably 0.5 to 20mg/m2. Most preferably, a treatment agent is added to the calcium carbonate containing material and/or the magnesium carbonate containing material of step a) such that the total weight of the treatment agent added in step c) is from 0.7 to 15mg/m, based on the calcium carbonate containing material and/or the magnesium carbonate containing material of step a)2。
Additionally or alternatively, the treating agent of step b) is added in step c) in an amount of 0.01 to 80.0 weight-%, based on the dry weight of the calcium carbonate-comprising material and/or the magnesium carbonate-comprising material of step a). Preferably, the treating agent of step b) is added in step c) in an amount of 0.01 to 40.0 weight-%, more preferably 0.1 to 20.0 weight-% and most preferably 0.5 to 10.0 weight-%, based on the dry weight of the calcium carbonate-comprising material and/or the magnesium carbonate-comprising material of step a).
The step of combining the calcium carbonate-comprising material and/or the magnesium carbonate-comprising material of step a) with the treating agent of step b) in one or more steps is preferably performed under mixing conditions. The skilled person will vary these mixture conditions (e.g. configuration of the mixing pallets and mixing speed) depending on his process equipment.
For example, the mixing can be carried out by means of a plowshare mixer. The plowshare mixer functions by the principle of a mechanically produced fluidized bed. The plowshare blades rotate adjacent to the horizontal cylindrical drum and carry the mixture components out of the product bed into the open mixing space. Mechanically produced fluidized beds ensure intensive mixing even in large batches in a very short time. A chopper and/or disperser are used to disperse the agglomerates in a dry operation. The apparatus used in the process of the invention can be selected, for example, from Gebr ü der
Figure BDA0001711391020000271
Maschinenbau GmbH, Germany or from VISCO JET Ru hrsysteme GmbH, Germany or from MTI Mischtechnik International GmbH, Germany.
In one embodiment, the process is carried out in a continuous mode. In this case, it is possible to add the treating agent to the calcium carbonate-comprising material and/or the magnesium carbonate-comprising material of step a) at a constant flow, such that a constant concentration of the treating agent is provided during step c).
Optionally, a treatment agent is added in one step to the calcium carbonate containing material and/or the magnesium carbonate containing material of step a), wherein the treatment agent is preferably added in one portion.
In another embodiment the process may be carried out in batch mode, i.e. the treatment agent is added to the calcium carbonate-comprising material and/or the magnesium carbonate-comprising material of step a) in more than one step, wherein the treatment agent is preferably added in approximately equal portions. Alternatively, it is also possible to add the treatment agent to the calcium carbonate-comprising material and/or the magnesium carbonate-comprising material of step a) in unequal portions, i.e. in larger and smaller portions.
According to one embodiment of the invention, step c) is carried out in a batch or continuous process for 0.1 to 1000 seconds. For example, step c) is a continuous process and comprises one or several contacting steps and the total contacting time is from 0.1 to 20 seconds, preferably from 0.5 to 15 seconds and most preferably from 1 to 10 seconds.
In order to obtain a sufficient combination of the calcium carbonate-comprising material and/or the magnesium carbonate-comprising material of step a) and the treatment agent of step b), it is necessary to perform the combining step c) at a temperature of 10 to 200 ℃. For example, the combining step c) is carried out at a temperature of from 20 to 150 ℃, more preferably from 20 to 120 ℃, even more preferably from 20 to 100 ℃ and most preferably from 20 to 80 ℃. It will be appreciated that the temperature at which the combining step c) is carried out is preferably adapted to the particular treating agent used. According to one embodiment, the treating agent of step b) is in liquid form, i.e. pure liquid or diluted/dissolved/dispersed solution/suspension/dispersion, or in molten form.
If the treating agent of step b) is in the form of a pure liquid or a diluted/dissolved solution at 25 ℃ and ambient pressure, the combining step c) is therefore preferably carried out at a temperature of from 10 to 40 ℃, preferably from 20 to 40 ℃, more preferably from 25 to 35 ℃ and most preferably about 30 ℃ (± 2 ℃).
Alternatively, the combining step c) may be carried out at a temperature of from 40 to 200 ℃, preferably from 50 to 150 ℃, more preferably from 60 to 120 ℃ and most preferably from 80 to 120 ℃.
According to one embodiment, the calcium carbonate-comprising material and/or the magnesium carbonate-comprising material provided in step a) and/or the treatment agent of step b) is preheated before performing step c). For example, the calcium carbonate-comprising material and/or the magnesium carbonate-comprising material provided in step a) or the treating agent of step b) is preheated before performing step c). Preferably, the calcium carbonate-comprising material and/or the magnesium carbonate-comprising material provided in step a) is preheated before performing step c).
For example, the calcium carbonate-comprising material and/or the magnesium carbonate-comprising material provided in step a) is preheated before performing step c). I.e. preheating the calcium carbonate-comprising material and/or the magnesium carbonate-comprising material of step a) at a temperature of 30 to 120 ℃.
The treatment time for carrying out the pre-heating of the calcium carbonate-comprising material and/or the magnesium carbonate-comprising material of step a) is 30 minutes or less, preferably 20 minutes or less and most preferably 15 minutes or less, such as 5 to 15 minutes.
In one embodiment of the present invention, the preheating of the calcium carbonate-comprising material and/or the magnesium carbonate-comprising material of step a) is performed at a temperature approximately equal to the temperature achieved during the combining step c).
The term "equal" temperature in the meaning of the present invention refers to a preheating temperature which is at most 20 ℃, preferably at most 15 ℃, more preferably 10 ℃ and most preferably at most 5 ℃ lower or higher than the temperature achieved during the combining step c).
The preheating of the calcium carbonate-comprising material and/or the magnesium carbonate-comprising material of step a) is preferably carried out under mixing conditions. The skilled person will vary these mixture conditions (e.g. configuration of the mixing pallets and mixing speed) depending on his process equipment.
In one embodiment, the combining step c) is carried out for at least 1 minute, preferably at least 5 minutes, such as at least 10 minutes, 15 minutes, 20 minutes, 30 minutes or 45 minutes. Additionally or alternatively, the combining step c) is carried out for at most 60 minutes, preferably at most 45 minutes, for example at most 30 minutes.
For example, combining step c) is carried out for a period of time ranging from 1 minute to 60 minutes, preferably for a period of time ranging from 10 minutes to 45 minutes, and most preferably for a period of time ranging from 10 minutes to 30 minutes. For example, the combining step c) is carried out for 20 minutes ± 5 minutes.
It will be appreciated that the combining step c) is preferably carried out at a temperature in the range of from 20 to 120 ℃ for a period of time in the range of from 1 minute to 60 minutes.
In one embodiment, the surface-treated calcium carbonate-comprising material and/or the magnesium carbonate-comprising material obtained in step c) is dried. This optional step is preferably performed in order to reduce the water content of the surface-treated calcium carbonate-comprising material and/or the magnesium carbonate-comprising material. Thus, the water content of the dried surface-treated calcium carbonate-comprising material and/or the magnesium carbonate-comprising material is lower than the water content of the surface-treated calcium carbonate-comprising material and/or the magnesium carbonate-comprising material prior to the drying step.
According to one embodiment, the method thus comprises the further step of drying the surface-treated calcium carbonate-comprising material and/or the magnesium carbonate-comprising material.
For example, the optional drying step is carried out at a temperature in the range of from 40 to 200 ℃, preferably from 50 to 150 ℃, more preferably from 60 to 120 ℃ and most preferably from 80 to 120 ℃, at ambient or reduced pressure until the water content of the obtained surface-treated calcium carbonate-comprising material and/or magnesium carbonate-comprising material is in the range of from 0.001 to 20 weight-%, based on the total weight of the surface-treated calcium carbonate-comprising material and/or magnesium carbonate-comprising material.
It will be appreciated that the optional drying step is carried out at ambient or reduced pressure. Preferably, the drying is carried out at ambient pressure.
Thus, the optional drying step is preferably carried out at a temperature in the range of 40 to 200 ℃ at ambient pressure. For example, the optional drying step is carried out at ambient pressure at a temperature in the range of from 50 to 150 ℃, preferably from 60 to 120 ℃ and more preferably from 80 to 120 ℃.
In one embodiment, the optional drying step is carried out until the water content of the obtained surface-treated calcium carbonate-comprising material and/or magnesium carbonate-comprising material is in the range of from 0.005 to 15 weight-%, preferably in the range of from 0.01 to 10 weight-% and more preferably in the range of from 0.05 to 5 weight-%, based on the total weight of the surface-treated calcium carbonate-comprising material and/or magnesium carbonate-comprising material.
Other reaction step
The method for preparing the surface-treated calcium carbonate-comprising material and/or the magnesium carbonate-comprising material according to the invention may comprise a further step d) of treating the surface-treated calcium carbonate-comprising material and/or the magnesium carbonate-comprising material obtained in step c) with at least one extender which is a hydrophobizing agent as defined above. If the method comprises step d), it will be appreciated that step d) is performed after the combining step c).
Use of surface-treated calcium carbonate-containing material and/or magnesium carbonate-containing material
The surface-treated calcium carbonate-containing material and/or magnesium carbonate-containing material according to the present invention may be used as an oxygen scavenger.
With regard to the definition of the surface-treated calcium carbonate-comprising material and/or the magnesium carbonate-comprising material and preferred embodiments thereof, reference is made to the statements provided above.
The inventors have surprisingly found that surface treated calcium carbonate-comprising materials and/or magnesium carbonate-comprising materials provide efficient oxygen (O) removal2) And in particular improved oxygen scavenging (O) compared to known oxygen scavenging materials2). Furthermore, the surface-treated calcium carbonate-comprising material and/or the magnesium carbonate-comprising material according to the invention provide permanent oxygen (O) removal2) Action and/or addition of per unit of scavenger enables the removal of large amounts of oxygen from the environment.
According to one embodiment of the invention, the total volume of oxygen reacted per gram of surface treatment agent is in the range of 0.01 to 50mL per day per gram of surface treatment agent and preferably in the range of 0.1 to 25mL per day per gram of surface treatment agent and more preferably in the range of 0.4 to 10mL per day per gram of surface treatment agent, wherein the reaction with oxygen is carried out with 500g of dry surface-treated calcium carbonate-containing material and/or magnesium carbonate-containing material in a volume of 7L, in an enclosed air-filled dryer at normal pressure.
Furthermore, the surface-treated calcium carbonate-containing material and/or magnesium carbonate-containing material according to the present invention is non-toxic, can be easily handled and can be used in various applications.
The treated surface-reacted calcium carbonate may be used in a variety of applications in view of its oxygen-scavenging properties. For example, the treated surface-reacted calcium carbonate may be used in a polymer composition, a coating, preferably in a polymer or paper coating, more preferably in a paper coating, a food application, a filter and/or a cosmetic application, preferably in a food application and more preferably in a food packaging application.
The scope and benefits of the present invention will be better understood on the basis of the following examples, which are intended to illustrate certain embodiments of the invention, but not to limit it.
Examples
1 measurement method
In the following, the measurement method implemented in the embodiment will be described.
Susceptibility to moisture absorption
After exposure to an atmosphere of 10 and 85% relative humidity at a temperature of +23 ℃ (± 2 ℃) for 2.5 hours, respectively, the susceptibility to moisture absorption, in mg moisture/g, of the materials as referred to herein is determined. For this purpose, the sample was first kept at an atmosphere of 10% relative humidity for 2.5 hours, then the atmosphere was changed to 85% relative humidity, and the sample was kept at this relative humidity for 2.5 hours. The amount of moisture pick-up in mg moisture/sample g was then calculated using the weight gain at 10 and 85% relative humidity.
Dividing the susceptibility to moisture absorption in mg/g by m2The specific surface area in mg/g (calculated on the basis of the specific surface area BET) corresponds to the ratio in mg/sample m2Expressed as "normalized susceptibility to moisture absorption".
Solids content
The suspension solids content (also referred to as "dry weight") was determined using a moisture analyzer MJ33(Mettler-Toledo, Switzerland) with the following setup: drying temperature of 150 ℃, automatic shut-off if the mass does not vary more than 1mg within a period of 30 seconds, standard drying of 5 to 20g of suspension.
50Particle size distribution (diameter) of particulate material<Mass% of X particles) and weight median diameter (d)
The weight-median particle diameter and the particle diameter mass distribution of the particulate material are determined via sedimentation methods, i.e. analysis of the sedimentation behavior in a gravitational field. Using SedigraphTM5100 or SedigraphTM5120 the measurement is carried out.
The volume median particle diameter d of a particulate material, such as particulate powdered iron, is evaluated using a Malvern Mastersizer 2000Laser Diffraction System, Malvern Instruments plc, Great Britain, using Mie theory with a particle refractive index of 1.57 and an absorption index of 0.00550And particle diameter volume distribution. Alternatively, Sym may be usedMeasurements were performed with a HELOS particle size analyzer from patec, Germany. Assuming constant density throughout the particle size distribution, the measurement can be considered equal to the weight distribution, and reference is made to the measurement technique.
Methods and apparatus known to the skilled person are commonly used to determine the particle size of fillers and other particulate materials. In the presence of 0.1 weight-% Na4P2O7Is measured in an aqueous solution of (a). The sample was dispersed using a high speed stirrer and in the presence of ultrasound.
BET specific surface area of the Material
Throughout this document, the specific surface area (in m) of the mineral filler is determined using the BET method (using nitrogen as the adsorption gas) known to the skilled person (ISO 9277:2010)2In terms of/g). The total surface area of the mineral filler (in m) is then obtained by multiplying the specific surface area of the mineral filler before treatment by the mass (in g)2Meter).
Humidity of calcium carbonate
A10 g sample of the powder was heated in an oven at 150 ℃ until the mass was constant for 20 minutes. Mass loss has been determined gravimetrically and expressed as weight-% loss based on the initial sample mass. This mass loss is due to sample humidity.
Oxygen scavenging test
The oxygen scavenging test is performed by placing a certain amount of powder in a closed dryer equipped with an oxygen measuring device (GOX 100, GHM Messtechnik GmbH) and estimating the total amount of oxygen removed by the sample (or active substance) in grams, assuming that the gas obeys the ideal gas law and neglecting the volume occupied by the powder. Results are expressed as mL O2Powder g or mL O2Active substance g.
The calculation is performed using the following equation:
Figure BDA0001711391020000341
n(O2) N (gas) × 20.9/100
m(O2)＝n(O2)×M(O2)
V(O2 dryer) V (dryer) × 20.9/100
Suppose R is 8.314 J.K-1·mol-1
T＝295K
P＝101 300Pa
M(O2)＝32g.mol-1
O in air2％＝20.9％
The values presented in the experimental part were calculated as follows:
Figure BDA0001711391020000342
Figure BDA0001711391020000343
2 preparation of surface-treated calcium carbonate-containing Material and/or magnesium carbonate-containing Material
In the following description of the preparation of examples and comparative examples, the indication of weight in the form of "parts" means "parts by weight" in total unless otherwise specified.
2.1 surface treatment with unsaturated fatty acids
2.1.1 example 1 powder 1
1.00kg of dried ground calcium carbonate (d) from Italy502.6 μm, BET specific surface area 2.6m2/g) were placed in a high-speed mixer (MTI mixer, MTI Mischtechnik International GmbH, Germany) and adjusted by stirring for 10 minutes (3000rpm, 30 ℃). Thereafter, 100 parts of CaCO are introduced30.6 parts of linoleic acid (6g, Sigma-Aldrich (Germany), technical grade 60-74%) and stirring is continued for a further 20 minutes (30 ℃, 3000 rpm). The treatment level corresponds to about 2.3mg/m2. After that, the mixture was taken out. A hydrophobic white powder (powder 1) was obtained.
2.1.2 example 2-powder 2
1.00kg of dried ground calcium carbonate (d) from Italy502.6 μm, BET specific surface area 2.6m2/g) were placed in a high-speed mixer (MTI mixer, MTI Mischtechnik International GmbH, Germany) and adjusted by stirring for 10 minutes (3000rpm, 30 ℃). Thereafter, 100 parts of CaCO are introduced31.0 part of linoleic acid (10g, Sigma-Aldrich (Germany), technical grade 60-74%) and stirring is continued for a further 20 minutes (30 ℃, 3000 rpm). The treatment level corresponds to about 3.8mg/m2. After that, the mixture was taken out. A hydrophobic white powder (powder 2) was obtained.
2.1.3 example 3 powder 3
1.00kg of dried ground calcium carbonate (d) from Italy502.6 μm, BET specific surface area 2.6m2/g) were placed in a high-speed mixer (MTI mixer, MTI Mischtechnik International GmbH, Germany) and adjusted by stirring for 10 minutes (3000rpm, 30 ℃). Thereafter, 100 parts of CaCO are introduced33 parts of linoleic acid (30g, Sigma-Aldrich (Germany), technical grade 60-74%) and stirring is continued for a further 20 minutes (30 ℃, 3000 rpm). The treatment level corresponds to about 11.5mg/m2. After that, the mixture was taken out. A hydrophobic white powder (powder 3) was obtained.
2.1.4 example 4-powder 4
1.00kg of dried ground calcium carbonate (d) from Italy502.6 μm, BET specific surface area 2.6m2/g) were placed in a high-speed mixer (MTI mixer, MTI Mischtechnik International GmbH, Germany) and adjusted by stirring for 10 minutes (3000rpm, 30 ℃). Thereafter, 100 parts of CaCO are introduced30.6 parts of oleic acid (6g, Fluka (Belgium)) and stirring is continued for a further 20 minutes (30 ℃, 3000 rpm). The treatment level corresponds to about 2.3mg/m2. After that, the mixture was taken out. A hydrophobic white powder (powder 4) was obtained.
2.1.5 example 5 powder 5
1.00kg of dry heavy carbon from ItalyCalcium (d)502.6 μm, BET specific surface area 2.6m2/g) were placed in a high-speed mixer (MTI mixer, MTI Mischtechnik International GmbH, Germany) and adjusted by stirring for 10 minutes (3000rpm, 30 ℃). Thereafter, 100 parts of CaCO are introduced31.0 part of oleic acid (10g, Alfa Aesar (Germany), technical grade, 90%) and stirring is continued for a further 20 minutes (30 ℃, 3000 rpm). The treatment level corresponds to about 3.8mg/m2. After that, the mixture was taken out. A hydrophobic white powder (powder 5) was obtained.
2.1.6 example 6-powder 6
1.00kg of dried ground calcium carbonate (d) from Italy502.6 μm, BET specific surface area 2.6m2/g) were placed in a high-speed mixer (MTI mixer, MTI Mischtechnik International GmbH, Germany) and adjusted by stirring for 10 minutes (3000rpm, 30 ℃). Thereafter, 100 parts of CaCO are introduced33 parts of oleic acid (30g, Fluka (Belgium)) and stirring is continued for a further 20 minutes (30 ℃, 3000 rpm). The treatment level corresponds to about 11.5mg/m2. After that, the mixture was taken out. A hydrophobic white powder (powder 6) was obtained.
2.1.7 example 7-powder 7
1.00kg of dried ground calcium carbonate (d) from Italy501.7 μm, BET specific surface area 3.8m2/g) were placed in a high-speed mixer (MTI mixer, MTI Mischtechnik International GmbH, Germany) and adjusted by stirring for 10 minutes (3000rpm, 30 ℃). Thereafter, 100 parts of CaCO are introduced31.0 part of oleic acid (10g, Fluka (Belgium)) and stirring is continued for a further 20 minutes (30 ℃, 3000 rpm). The treatment level corresponds to about 2.6mg/m2. After that, the mixture was taken out. A hydrophobic white powder (powder 7) was obtained.
2.2 surface treatment with ascorbic acid
2.2.1 example 8-powder 8
700g of dry ground calcium carbonate (d) from Italy501.7 μm, BET specific surface area 3.8m2/g) were placed in a high-speed mixer (MTI mixer, MTI Mischtechnik International GmbH, Germany) and adjusted by stirring for 10 minutes (3000rpm, 30 ℃). Thereafter, 100 parts of CaCO was added31.0 part of (L) -ascorbic acid (reagent grade, Sigma life science, China, 31g of a previously prepared 22.6% solids aqueous solution) and stirring is continued for a further 20 minutes (100 ℃, 3000 rpm). The treatment level corresponds to about 2.6mg/m2. Thereafter, the mixture was cooled and removed from the mixer. A coloured (beige-yellow) powder (powder 8) was obtained.
2.2.2 example 9 slurry 9
600g (100 parts) of moist ground calcium carbonate (d) from Carrara, Italy in 2L bottles501.6 μm, BET specific surface area 4.1m2440g of water are added and 0.46 part of a polyacrylate dispersant (2.76g of a 42% by weight aqueous solution of 100% sodium-neutralized polyacrylate, M) is added dropwise at room temperature under vigorous stirring (930rpm) (Pendraulik stirrer)w3500 g/mol, pH 8). Once a stable suspension is obtained, 1.0 part of ascorbic acid (6g, reagent grade, Sigma life science) is added at room temperature (this treatment level corresponds to about 2.4 mg/m)2) And stirring was continued for 10 minutes. The mixture became thicker (slurry 9).
2.3 surface treatment with Gallic acid
2.3.1 example 10-powder 10
700g of dry ground calcium carbonate (d) from Italy502.6 μm, BET specific surface area 2.6m2/g) were placed in a high-speed mixer (MTI mixer, MTI Mischtechnik International GmbH, Germany) and adjusted by stirring for 10 minutes (3000rpm, 80 ℃). Thereafter, 100 parts of CaCO was added31.0 part of gallic acid (Sigma-Aldrich, 35g of a previously prepared solution at 20% solids content in ethanol) and stirring is continued for a further 10 minutes at 80 ℃ and then for 10 minutes at 100 ℃ and again for 20 minutes at 80 ℃ (3000 rpm). The treatment level corresponds to about 3.8mg/m2. Thereafter, the mixture was cooled and taken out of the mixer. A coloured (grey-green) powder (powder 10) was obtained.
2.4 surface treatment with iron
2.4.1 example 11 slurry 11
600g (100 parts) of wet-milled and spray-dried marble from Carla Italy in a 2L bottle (d)501.6 μm, BET specific surface area 4.1m2Per g) 300g of water are added and 0.23 part of a polyacrylate dispersant (1.38g of a 42% strength by weight aqueous solution of 100% sodium-neutralized polyacrylate, M) is added dropwise at room temperature under vigorous stirring (930rpm) (Pendraulik stirrer)w3500 g/mol, pH 8). Once a stable suspension is obtained, 1.0 part of iron nanopowder (6g, 60-80nm particle size, Aldrich (China)) is added at room temperature. The treatment level corresponds to about 2.4mg/m2. The mixture turned grey in color and a stable slurry (slurry 11) was obtained.
2.5 comparative example
2.5.1 comparative example 1-powder CE1
Powder CE1 is dry ground calcium carbonate (d) from Italy502.6 μm, BET specific surface area 2.6m2/g)。
2.5.2 comparative example 2-powder CE2
Powder CE2 is dry ground calcium carbonate (d) from Italy501.7 μm, BET specific surface area 3.8m2/g)。
2.5.3 comparative example 3-CE3
CE3 is commercially available linoleic acid (Sigma-Aldrich (Germany), technical grade 60-74%).
2.5.4 comparative example 4-powder CE4
Powder CE4 is a commercially available (L) -ascorbic acid crystal powder (Sigma life science, reagent grade, China).
2.5.5 comparative example 5-slurry CE5
Wet milling and spraying 600g (100 parts) from Carla Italy in a 2L bottleFog-dried marble (d)501.6 μm, BET specific surface area 4.1m2Per g) 300g of water are added and 0.23 part of a dispersant (1.38g of a 42% strength by weight aqueous solution of 100% sodium-neutralized polyacrylate, M.sub.w3500 g/mol, pH 8). After stirring for about 10 minutes, a stable slurry (slurry CE5) was obtained.
2.5.6 comparative example 6-CE6
Powder CE6 is a commercially available oleic acid (fluka (belgium)).
Table 1: summary of the prepared surface-treated calcium carbonate-containing material.
Figure BDA0001711391020000391
Figure BDA0001711391020000401
Table 2: water absorption rate
Examples Water absorption (mg/g)
CE1 1.8
CE2 2.8
2 0.7
4 0.4
5 0.5
6 0.7
7 0.6
3 coating pigment preparation and paper coating
Examples 12 to 13(E12 to E13) and comparative example 12(CE12)
Slurries according to examples 9 and 11 and comparative example 5 were then used to prepare a slurry containing 100 parts CaCO3(w/w) and 6 or 12 parts (dry/dry) of a synthetic binder based on styrene-butadiene copolymers (Styronal D628(BASF, Germany)) and is applied to the coating colour from Fischer Papier AG, Switzerland
Figure BDA0001711391020000403
On both sides of the foil (thickness 80 μm, size: 18X 26 cm)2，62g/m2Polypropylene) and dried on a belt dryer (150 ℃). Immediately after coating, the sheets were stored in closed plastic bags to limit oxygen exposure until use. The composition of the coating pigments and the coating weights are summarized in table 3 below.
Table 3: coating color preparation and coating weight.
Figure BDA0001711391020000402
Figure BDA0001711391020000411
4 oxygen removal test
4.1 testing of the powders
The oxygen scavenging test was carried out by placing a defined amount of the powder in a closed dryer equipped with an oxygen measuring device (GOX 100, GHM Messtechnik GmbH, Germany). The relative amount of oxygen in the air is periodically recorded and the total amount of oxygen removed by the sample in grams is estimated, assuming that the gas obeys the ideal gas law and neglecting the volume occupied by the powder. Results are expressed as mL O2Powder g.
4.1.1 example 14
500g of the powder from example 1 are placed in a 7L sealed desiccator and the O is recorded periodically2Amount of the compound (A). The treatment level corresponds to about 2.3mg/m2。
Table 4: oxygen scavenging test.
Figure BDA0001711391020000412
The results of example 14 are also shown in FIGS. 1 and 2.
4.1.2 example 15
500g of the powder from example 2 are placed in a sealed 7L desiccator and the O is recorded periodically2Amount of the compound (A). The treatment level corresponds to about 3.8mg/m2。
Table 5: oxygen scavenging test.
Time [ h ]] 0 1 2.5 3.5 4.6 5.5 6.5 7.75
O in the dryer2[％] 20.9 20.8 20.7 20.6 20.4 20.3 20.2 20
Eliminated O2(mL/g powder) 0 0.014 0.028 0.042 0.07 0.084 0.098 0.126
Eliminated O2(mL/g linoleic acid) 0 1.41 2.83 4.24 7.07 8.48 9.90 12.73
Time [ h ]] 23 24 28 32.5 47.3 51 56 120
O in the dryer2[％] 16.8 16.6 16 15.3 14.7 14.4 14.2 13.6
Eliminated O2(mL/g powder) 0.574 0.602 0.686 0.784 0.868 0.91 0.938 1.022
Eliminated O2(mL/g linoleic acid) 57.98 60.81 69.29 79.19 87.68 91.92 94.75 103.23
The results of example 15 are also shown in figures 1 and 2.
4.1.3 example 16
500g of the powder from example 3 are placed in a sealed 7L desiccator and the O is recorded periodically2Amount of the compound (A). The treatment level corresponds to about 11.5mg/m2。
Table 6: oxygen scavenging test.
Time [ h ]] 0 2 4 5.5 20 29 44 68
O in the dryer2[％] 20.9 20.8 20.5 20.3 17.8 14.8 8.1 0.4
Eliminated O2(mL/g powder) 0 0.014 0.056 0.084 0.434 0.854 1.792 2.87
Eliminated O2(mL/g linoleic acid) 0 0.48 1.92 2.88 14.90 29.33 61.54 98.56
Note that: the test was terminated after 68 hours because all the oxygen in the seal dryer had been consumed.
The results of example 16 are also shown in FIGS. 1 and 2.
4.1.4 example 17
500g of the powder from example 4 are placed in a sealed 7L desiccator and the O is recorded periodically2Amount of the compound (A). The treatment level corresponds to about 2.3mg/m2。
Table 7: oxygen scavenging test.
Figure BDA0001711391020000421
Figure BDA0001711391020000431
The results of example 17 are also shown in FIGS. 3 and 5.
4.1.5 example 18
500g of the powder from example 5 are placed in a sealed 7L desiccator and the O is recorded periodically2Amount of the compound (A). The treatment level corresponds to about 3.8mg/m2。
Table 8: oxygen scavenging test.
Figure BDA0001711391020000432
The results of example 18 are also shown in FIGS. 3 and 5.
4.1.6 example 19
500g of the powder from example 6 are placed in a sealed 7L dryer and the O is recorded periodically2Amount of the compound (A). The treatment level corresponds to about 11.5mg/m2。
Table 9: oxygen scavenging test.
Figure BDA0001711391020000433
Figure BDA0001711391020000441
The results of example 19 are also shown in FIGS. 3 and 5.
4.1.7 example 20
500g of the powder from example 7 are placed in a sealed 7L dryer and the O is recorded periodically2Amount of the compound (A). The treatment level corresponds to about 2.6mg/m2。
Table 10: oxygen scavenging test.
Figure BDA0001711391020000442
The results of example 20 are also shown in fig. 4 and 6.
4.1.8 example 21
500g of the powder from example 8 are placed in a sealed 7L desiccator and the O is recorded periodically2Amount of the compound (A). The treatment level corresponds to about 2.6mg/m2。
Table 11: oxygen scavenging test.
Figure BDA0001711391020000451
The results of example 21 are also shown in fig. 7 and 8.
4.1.9 example 22
500g of the powder from example 10 are placed in a sealed 7L dryer and the O is recorded periodically2Amount of the compound (A). The treatment level corresponds to about 3.8mg/m2。
Table 12: oxygen scavenging test.
Figure BDA0001711391020000452
The results of example 22 are also shown in FIG. 9.
4.1.10 comparative example 7
500g of the powder from example CE1 were placed in a sealed 7L desiccator and the O was recorded periodically2Amount of the compound (A). After 2 weeks O was not noticed2Significant changes in level.
Table 13: oxygen scavenging test.
Figure BDA0001711391020000461
The results of comparative example 7 are also shown in fig. 1.
4.1.11 comparative example 8
500g of the powder from example CE2 were placed in a 7L sealed desiccator and the O was recorded periodically2Amount of the compound (A). After 2 weeks O was not noticed2Significant changes in level.
4.1.12 comparative example 9
14.5g linoleic acid (CE3) was placed in a 50mL beaker and placed in a sealed 7L desiccator with periodic recording of O2Amount of the compound (A).
Table 14: oxygen scavenging test.
Figure BDA0001711391020000462
The results of comparative example 9 are also shown in fig. 2.
4.1.13 comparative example 10
10g of (L) -ascorbic acid crystal powder (Sigma life science, reagent grade, China, powder CE4) were placed in a sealed 7L desiccator and O was recorded periodically2Amount of the compound (A).
Table 15: oxygen scavenging test.
Figure BDA0001711391020000463
The results of comparative example 10 are also shown in fig. 7 and 8.
4.1.13 comparative example 11
14.5g of oleic acid (CE6) were placed in a sealed 7L desiccator and O was recorded periodically2Amount of the compound (A).
Table 16: oxygen scavenging test.
Figure BDA0001711391020000471
The results of comparative example 11 are also shown in fig. 5 and 6.
4.2 testing on coated paper
4.2.1 example 23: paper from E12 (containing ascorbic acid)
80 strips (5x18 cm)2) Coated paper E12 was cut into smaller pieces (4 pieces each) and placed in a sealed 2.9L desiccator, and O was recorded periodically2Amount of the compound (A). The estimated amount of coating (by weight) used for this test was 64 g.
Table 17: oxygen scavenging test.
Figure BDA0001711391020000472
The results of example 23 are also shown in fig. 10.
4.2.2 example 24: paper from E13 (containing elemental iron)
80 strips (5x18 cm)2) Coated paper E13 was cut into smaller pieces (4 pieces each) and placed in a sealed 2.9L desiccator, and O was recorded periodically2Amount of the compound (A). The estimated amount of coating (by weight) used in this test was 77 g.
Table 18: oxygen scavenging test.
Figure BDA0001711391020000481
The results of example 24 are also shown in FIG. 10.
4.2.3 comparative example 13: paper from CE12 (comparative example)
108 strips (5x18 cm)2) The coated paper CE12 was cut into smaller pieces (4 pieces each) and placed in a sealed 2.9L desiccator, and the O was recorded periodically2Amount of the compound (A). The estimated amount of coating (by weight) used in this test was 84 g.
Table 19: oxygen scavenging test.
Figure BDA0001711391020000482
The results of comparative example 13 are also shown in fig. 10.
All examples show that high removal of O can be achieved with surface treated calcium carbonate-comprising materials and/or magnesium carbonate-comprising materials2The value is obtained. Thus, the co-O may be enhanced by the use of a treating agent, possibly by increasing the available surface area2The reaction of (1).

Claims (38)

1.经表面处理的含碳酸钙的材料和/或含碳酸镁的材料作为除氧剂的用途；其中1. Use of surface-treated calcium carbonate-containing materials and/or magnesium carbonate-containing materials as oxygen scavengers; wherein 所述表面处理剂选自由以下组成的组：抗坏血酸和/或其盐、没食子酸和/或其盐、不饱和脂肪酸和/或其盐、元素铁、铁II盐和含铁II氧化物、含铁II和III氧化物及其混合物；并且其中The surface treatment agent is selected from the group consisting of ascorbic acid and/or its salts, gallic acid and/or its salts, unsaturated fatty acids and/or its salts, elemental iron, iron II salts and iron II containing oxides, containing Iron II and III oxides and mixtures thereof; and wherein 基于至少一种含碳酸钙的材料和/或含碳酸镁的材料，所述至少一种含碳酸钙的材料和/或含碳酸镁的材料的总表面积上的所述表面处理剂的总重量为0.01至40mg/m2并且其中The total weight of the surface treatment agent on the total surface area of the at least one calcium carbonate-containing material and/or magnesium carbonate-containing material, based on the at least one calcium carbonate-containing material and/or magnesium carbonate-containing material, is 0.01 to 40mg/ m2 and where 该经表面处理的含碳酸钙的材料和/或含碳酸镁的材料至少包含含碳酸钙的材料和/或含碳酸镁的材料，其已经与该表面处理剂接触，以便获得位于该含碳酸钙的材料和/或含碳酸镁的材料的至少一部分表面上的处理层，其中该处理层是指在该含碳酸钙的材料和/或含碳酸镁的材料的至少一部分表面上包含表面处理剂及其反应产物的层。The surface-treated calcium carbonate-containing material and/or magnesium carbonate-containing material comprises at least a calcium carbonate-containing material and/or a magnesium carbonate-containing material, which has been brought into contact with the surface treatment agent in order to obtain a The material and/or the treatment layer on the surface of at least a part of the material containing magnesium carbonate, wherein the treatment layer refers to the surface treatment agent and layer of its reaction product. 2.根据权利要求1所述的用途，其中所述含碳酸钙的材料和/或含碳酸镁的材料选自由以下组成的组：重质碳酸钙，沉淀碳酸钙，白云石及其混合物。2. The use according to claim 1, wherein the calcium carbonate-containing material and/or the magnesium carbonate-containing material is selected from the group consisting of ground calcium carbonate, precipitated calcium carbonate, dolomite and mixtures thereof. 3.根据权利要求2所述的用途，其中所述重质碳酸钙选自大理石、石灰石和/或白垩。3. The use according to claim 2, wherein the ground calcium carbonate is selected from marble, limestone and/or chalk. 4.根据权利要求2所述的用途，其中所述沉淀碳酸钙选自球文石、方解石和/或霰石。4. The use according to claim 2, wherein the precipitated calcium carbonate is selected from aragonite, calcite and/or aragonite. 5.根据权利要求2所述的用途，其中所述至少一种含碳酸钙的材料和/或含碳酸镁的材料选自由以下组成的组：白云质大理石、菱镁矿大理石、石灰石、白垩及其混合物。5. Use according to claim 2, wherein the at least one calcium carbonate-containing material and/or magnesium carbonate-containing material is selected from the group consisting of: dolomitic marble, magnesite marble, limestone, chalk and its mixture. 6.根据权利要求2所述的用途，其中所述至少一种含碳酸钙的材料和/或含碳酸镁的材料为重质碳酸钙。6. The use according to claim 2, wherein the at least one calcium carbonate-containing material and/or magnesium carbonate-containing material is ground calcium carbonate. 7.根据权利要求1-6任一项所述的用途，其中根据ISO 9277:2010使用氮和BET方法所测量的，所述至少一种含碳酸钙的材料和/或含碳酸镁的材料的比表面积(BET)为0.5至150m2/g。7. The use according to any one of claims 1 to 6, wherein the at least one calcium carbonate-containing material and/or magnesium carbonate-containing material has a The specific surface area (BET) is 0.5 to 150 m 2 /g. 8.根据权利要求7所述的用途，其中根据ISO 9277:2010使用氮和BET方法所测量的，所述至少一种含碳酸钙的材料和/或含碳酸镁的材料的比表面积(BET)为1至60m2/g。8. Use according to claim 7, wherein the specific surface area (BET) of the at least one calcium carbonate-containing material and/or magnesium carbonate-containing material measured according to ISO 9277:2010 using nitrogen and the BET method 1 to 60 m 2 /g. 9.根据权利要求7所述的用途，其中根据ISO 9277:2010使用氮和BET方法所测量的，所述至少一种含碳酸钙的材料和/或含碳酸镁的材料的比表面积(BET)为1.5至15m2/g。9. Use according to claim 7, wherein the specific surface area (BET) of the at least one calcium carbonate-containing material and/or magnesium carbonate-containing material measured using nitrogen and the BET method according to ISO 9277:2010 1.5 to 15 m 2 /g. 10.根据权利要求1-6任一项所述的用途，其中基于所述至少一种含碳酸钙的材料和/或含碳酸镁的材料，所述至少一种经表面处理的含碳酸钙的材料和/或含碳酸镁的材料的总表面积上的所述表面处理剂的总重量为0.1至40mg/m2。10. The use according to any one of claims 1 to 6, wherein the at least one surface-treated calcium carbonate-containing material is based on the at least one calcium carbonate-containing material and/or the magnesium carbonate-containing material. The total weight of the surface treatment agent on the total surface area of the material and/or the magnesium carbonate-containing material is 0.1 to 40 mg/m 2 . 11.根据权利要求10所述的用途，其中基于所述至少一种含碳酸钙的材料和/或含碳酸镁的材料，所述至少一种经表面处理的含碳酸钙的材料和/或含碳酸镁的材料的总表面积上的所述表面处理剂的总重量为0.5至20mg/m2。11. Use according to claim 10, wherein based on the at least one calcium carbonate-containing material and/or magnesium carbonate-containing material, the at least one surface-treated calcium carbonate-containing material and/or the The total weight of the surface treatment agent on the total surface area of the magnesium carbonate material is 0.5 to 20 mg/m 2 . 12.根据权利要求10所述的用途，其中基于所述至少一种含碳酸钙的材料和/或含碳酸镁的材料，所述至少一种经表面处理的含碳酸钙的材料和/或含碳酸镁的材料的总表面积上的所述表面处理剂的总重量0.7至15mg/m2。12. Use according to claim 10, wherein based on the at least one calcium carbonate-containing material and/or magnesium carbonate-containing material, the at least one surface-treated calcium carbonate-containing material and/or the The total weight of the surface treatment agent on the total surface area of the magnesium carbonate material is 0.7 to 15 mg/m 2 . 13.根据权利要求1-6任一项所述的用途，其中所述经表面处理的含碳酸钙的材料和/或含碳酸镁的材料的吸湿易感性为0.05至20mg/g。13. The use according to any one of claims 1-6, wherein the surface-treated calcium carbonate-containing material and/or magnesium carbonate-containing material has a susceptibility to moisture absorption of 0.05 to 20 mg/g. 14.根据权利要求13所述的用途，其中所述经表面处理的含碳酸钙的材料和/或含碳酸镁的材料的吸湿易感性为0.1至15mg/g。14. The use according to claim 13, wherein the hygroscopic susceptibility of the surface-treated calcium carbonate-containing material and/or magnesium carbonate-containing material is 0.1 to 15 mg/g. 15.根据权利要求13所述的用途，其中所述经表面处理的含碳酸钙的材料和/或含碳酸镁的材料的吸湿易感性为0.2至10mg/g。15. The use according to claim 13, wherein the hygroscopic susceptibility of the surface-treated calcium carbonate-containing material and/or magnesium carbonate-containing material is 0.2 to 10 mg/g. 16.根据权利要求1-6任一项所述的用途，其中所述不饱和脂肪酸选自由以下组成的组：油酸、亚油酸、亚麻酸、巴豆酸、肉豆蔻油酸、棕榈油酸、十六碳烯酸、反油酸、十八碳烯酸、鳕烯酸、芥酸、神经酸、二十碳二烯酸、二十二碳二烯酸、皮诺敛酸、桐油酸、蜂蜜酸、双高-γ-亚麻酸、二十碳三烯酸、硬脂四烯酸、花生四烯酸、二十碳四烯酸、肾上腺酸、十八碳五稀酸、二十碳五烯酸、奥唑酸、沙丁酸、二十四醇五烯酸、二十二碳六烯酸、鲱鱼酸、这些酸的盐及其混合物。16. The use of any one of claims 1-6, wherein the unsaturated fatty acid is selected from the group consisting of: oleic acid, linoleic acid, linolenic acid, crotonic acid, myristic acid, palmitoleic acid , hexadecenoic acid, elaidic acid, octadecenoic acid, codenoic acid, erucic acid, nervonic acid, eicosadienoic acid, docosadienoic acid, pinocolic acid, eleostearic acid, Honey acid, bihomo-gamma-linolenic acid, eicosatrienoic acid, stearic acid, arachidonic acid, eicosatetraenoic acid, adrenal acid, octadecosapentaenoic acid, eicosapenta Olenoic acid, oxazole acid, salbutyric acid, docosahexaenoic acid, herring acid, salts of these acids and mixtures thereof. 17.根据权利要求16所述的用途，其中所述不饱和脂肪酸为油酸或亚油酸。17. The use according to claim 16, wherein the unsaturated fatty acid is oleic acid or linoleic acid. 18.根据权利要求1-6任一项所述的用途，其中所述铁是体积中值粒子尺寸d50范围为5至10μm的颗粒态粉末铁。18. The use according to any one of claims 1-6, wherein the iron is granular powdered iron having a volume median particle size d50 in the range 5 to 10 [mu]m. 19.根据权利要求18所述的用途，其中所述铁是体积中值粒子尺寸d50范围为10nm至2μm的颗粒态粉末铁。19. The use according to claim 18, wherein the iron is granular powdered iron having a volume median particle size d50 in the range of 10 nm to 2 [mu]m. 20.根据权利要求18所述的用途，其中所述铁是体积中值粒子尺寸d50范围为30nm至500nm的颗粒态粉末铁。20. The use of claim 18, wherein the iron is particulate powdered iron having a volume median particle size d50 ranging from 30 nm to 500 nm. 21.根据权利要求1-6任一项所述的用途，其中所述含碳酸钙的材料和/或含碳酸镁的材料另外用另一种添加剂处理。21. The use according to any one of claims 1-6, wherein the calcium carbonate-containing material and/or the magnesium carbonate-containing material is additionally treated with another additive. 22.根据权利要求21所述的用途，其中所述含碳酸钙的材料和/或含碳酸镁的材料另外用分散剂、粘合剂和/或活化剂处理。22. The use according to claim 21, wherein the calcium carbonate-containing material and/or the magnesium carbonate-containing material is additionally treated with dispersants, binders and/or activators. 23.根据权利要求22所述的用途，其中所述分散剂是聚丙烯酸酯分散剂。23. The use according to claim 22, wherein the dispersant is a polyacrylate dispersant. 24.根据权利要求21所述的用途，其中所述含碳酸钙的材料和/或含碳酸镁的材料另外用粘合剂和/或活化剂处理。24. The use according to claim 21, wherein the calcium carbonate-containing material and/or the magnesium carbonate-containing material is additionally treated with a binder and/or an activator. 25.根据权利要求1-6任一项所述的用途，其中每克表面处理剂反应的氧总体积在每天每克表面处理剂0.01至10mL范围内，其中与氧的反应用500g干燥的经表面处理的含碳酸钙的材料和/或含碳酸镁的材料在体积为7L的充满空气的封闭干燥器内在正常压力下进行。25. The use of any one of claims 1-6, wherein the total volume of oxygen reacted per gram of surface treatment agent is in the range of 0.01 to 10 mL per gram of surface treatment agent per day, wherein the reaction with oxygen is performed with 500 g of dried The surface treatment of the calcium carbonate-containing material and/or the magnesium carbonate-containing material was carried out under normal pressure in a closed desiccator filled with air with a volume of 7 L. 26.根据权利要求25所述的用途，其中每克表面处理剂反应的氧总体积在每天每克表面处理剂0.1至8mL范围内，其中与氧的反应用500g干燥的经表面处理的含碳酸钙的材料和/或含碳酸镁的材料在体积为7L的充满空气的封闭干燥器内在正常压力下进行。26. Use according to claim 25, wherein the total volume of oxygen reacted per gram of surface treatment agent is in the range of 0.1 to 8 mL per gram of surface treatment agent per day, wherein the reaction with oxygen is carried out with 500 g of dry surface-treated carbonic acid containing The calcium and/or magnesium carbonate-containing material was carried out under normal pressure in an air-filled closed desiccator with a volume of 7 L. 27.根据权利要求25所述的用途，其中每克表面处理剂反应的氧总体积在每天每克表面处理剂0.4至6mL范围内，其中与氧的反应用500g干燥的经表面处理的含碳酸钙的材料和/或含碳酸镁的材料在体积为7L的充满空气的封闭干燥器内在正常压力下进行。27. The use according to claim 25, wherein the total volume of oxygen reacted per gram of surface treatment agent is in the range of 0.4 to 6 mL per gram of surface treatment agent per day, wherein the reaction with oxygen is carried out with 500 g of dry, surface-treated carbonic acid containing The calcium and/or magnesium carbonate-containing material was carried out under normal pressure in an air-filled closed desiccator with a volume of 7 L. 28.根据权利要求1-6任一项所述的用途，其中所述经表面处理的含碳酸钙的材料和/或含碳酸镁的材料还包含至少一种为疏水剂的补充剂，其至少部分覆盖所述经表面处理的含碳酸钙的材料和/或含碳酸镁的材料，其中基于所述至少一种含碳酸钙的材料和/或含碳酸镁的材料，所述经表面处理的含碳酸钙的材料和/或含碳酸镁的材料的总表面积上的所述至少一种疏水剂的总重量为0.001至10mg/m2。28. The use of any one of claims 1-6, wherein the surface-treated calcium carbonate-containing material and/or magnesium carbonate-containing material further comprises at least one extender that is a hydrophobic agent, which at least The surface-treated calcium carbonate-containing material and/or the magnesium carbonate-containing material is partially covered, wherein the surface-treated calcium carbonate-containing material and/or the magnesium carbonate-containing material is partially covered based on the at least one calcium carbonate-containing material and/or the magnesium carbonate-containing material. The total weight of the at least one hydrophobic agent on the total surface area of the calcium carbonate material and/or the magnesium carbonate-containing material is from 0.001 to 10 mg/m 2 . 29.根据权利要求28所述的用途，其中基于所述至少一种含碳酸钙的材料和/或含碳酸镁的材料，所述经表面处理的含碳酸钙的材料和/或含碳酸镁的材料的总表面积上的所述至少一种疏水剂的总重量为0.001至9mg/m2。29. The use according to claim 28, wherein the surface-treated calcium carbonate-containing material and/or magnesium carbonate-containing material is based on the at least one calcium carbonate-containing material and/or magnesium carbonate-containing material. The total weight of the at least one hydrophobic agent on the total surface area of the material is from 0.001 to 9 mg/m 2 . 30.根据权利要求28所述的用途，其中基于所述至少一种含碳酸钙的材料和/或含碳酸镁的材料，所述经表面处理的含碳酸钙的材料和/或含碳酸镁的材料的总表面积上的所述至少一种疏水剂的总重量为0.01至8mg/m2。30. Use according to claim 28, wherein the surface-treated calcium carbonate-containing material and/or magnesium carbonate-containing material is based on the at least one calcium carbonate-containing material and/or magnesium carbonate-containing material The total weight of the at least one hydrophobic agent on the total surface area of the material is 0.01 to 8 mg/m 2 . 31.根据权利要求28所述的用途，其中基于所述至少一种含碳酸钙的材料和/或含碳酸镁的材料，所述经表面处理的含碳酸钙的材料和/或含碳酸镁的材料的总表面积上的所述至少一种疏水剂的总重量为0.1至4mg/m2。31. The use according to claim 28, wherein the surface-treated calcium carbonate-containing material and/or magnesium carbonate-containing material is based on the at least one calcium carbonate-containing material and/or magnesium carbonate-containing material. The total weight of the at least one hydrophobic agent on the total surface area of the material is 0.1 to 4 mg/m 2 . 32.根据权利要求28所述的用途，其中所述经表面处理的含碳酸钙的材料和/或含碳酸镁的材料包含至少一种为疏水剂的补充剂，所述疏水剂选自由以下组成的组：碳原子总量为C4至C24的脂肪族羧酸和/或其反应产物，由经选自取代基中碳原子总量为至少C2至C30的直链、支链、脂肪族和环状基团的基团单取代的琥珀酸酐组成的单取代琥珀酸酐和/或其反应产物，一种或多种磷酸单酯和/或其反应产物与一种或多种磷酸二酯和/或其反应产物的磷酸酯掺混物，聚氢硅氧烷及其反应产物，惰性硅油及其混合物。32. Use according to claim 28, wherein the surface-treated calcium carbonate-containing material and/or magnesium carbonate-containing material comprises at least one extender that is a hydrophobic agent selected from the group consisting of The group of: aliphatic carboxylic acids and/or their reaction products with total carbon atoms ranging from C 4 to C 24 , by being selected from the straight chain, branched chain, Monosubstituted succinic anhydrides consisting of monosubstituted succinic anhydrides of aliphatic and cyclic groups and/or their reaction products, one or more phosphoric acid monoesters and/or their reaction products with one or more phosphoric acid dibasic Phosphate ester blends of esters and/or reaction products thereof, polyhydrogensiloxanes and reaction products thereof, inert silicone oils and mixtures thereof. 33.根据权利要求32所述的用途，其中所述惰性硅油为聚二甲基硅氧烷。33. The use of claim 32, wherein the inert silicone oil is polydimethylsiloxane. 34.根据权利要求1-6任一项所述的用途，其用于聚合物组合物、涂层中、食品应用、过滤器和/或化妆品应用中。34. The use of any one of claims 1-6 in polymer compositions, coatings, food applications, filters and/or cosmetic applications. 35.根据权利要求34所述的用途，其用于聚合物或纸涂层中。35. The use of claim 34 in polymer or paper coatings. 36.根据权利要求34所述的用途，其用于纸涂层中。36. The use according to claim 34 in paper coating. 37.根据权利要求34所述的用途，其用于食品应用中。37. The use of claim 34 in food applications. 38.根据权利要求34所述的用途，其用于食品包装应用中。38. The use of claim 34 in food packaging applications.
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